University of Cyprus

2023 Joint CTMNM/NAGC Conference

8-12 May 2023, Anargyrios and Korgialenios School of

Spetses, Spetses Island, Greece

CTMNM and NAGC are two series of workshops, organized since 2005 by Professor
George Christou (University of Florida/USA), Professor Spyros Perlepes (University ofPatras/Greece), Professor Anastasios Tasiopoulos (University of Cyprus/NicosiaCyprus), and a group of scientists from the Institute of Nanoscience and Nanotechnology(INN, NCSR Demokritos, Athens/Greece). The NAGC and CTMNM workshops are held
every two years and have both grown to be extremely popular with broad range ofscientists.
This is the second joint meeting and will bring together distinguished experts and younger
researchers working in diverse fields and applications of molecular and nanoscale
magnetism and on paramagnetic materials as well. The program will thus span chemistry,
physics, material science and biochemistry using experimental or advanced theoreticalmethods. For the maximum benefit of all participants it is expected that senior speakers
will present talks that have a tutorial component to them. We also encourage students
and postdocs to attend the meeting and we will try to ensure that as many as possible will
be included in the program. The meeting will be hosted at Anargyreios and Korgialenios
School of Spetses which is located at the island of Spetses at Argosaronikos Gulf,
Greece. The accommodation and lecture facilities are situated within the campus of the
School.
Committees
International Organizing Committee
Prof. George Christou, Dept. of Chemistry, Univ. of Florida, USA
Dr. Georgios Papavassiliou, INN, NCSR “Demokritos” Greece
Prof. Spyros P. Perlepes, Dept. Of Chemistry, Univ. of Patras, Greece
Prof. Anastasios J. Tasiopoulos, Dept. Chemistry, Univ. of Cyprus, Cyprus
Local Organizing Committee
Dr Vassilis Psycharis, INN, NCSR “Demokritos”, Greece.
Dr Georgios Papavassiliou, INN, NCSR “Demokritos”, Greece.
Dr Catherine P. Raptopoulou, INN, NCSR “Demokritos”, Greece.
Dr Yiannis Sanakis, INN, NCSR “Demokritos”, Greece.
Dr George Mitrikas, INN, NCSR “Demokritos”, Greece.
Prof. Spyros P. Perlepes, Dept. Of Chemistry, Univ. of Patras, Greece

REGISTRATION
Registration desk
The registration desk will be open on Sunday, May 7, 2023 from 16:00 to 19:00, at theAnargyrios and Korgialenios School where the welcome reception will take place. It will
also open on Monday morning at the School where the lectures will take place. There is
no registration fee for the participants.
SCIENTIFIC PROGRAM
All presentations will be oral (30 and 15 minutes including discussion). Computer-screen
projection (for PowerPoint) will be available. The timetable given in the following pages
may be subjected to small alterations.
SOCIAL PROGRAM
Reception
The reception (welcome party) will take place, on Sunday May 7th, at the Anargyreios andKorgialenios School at 20:00. All registered persons (participants and accompanying
members) are cordially invited.
Official Dinner – Greek night
The official dinner of the conference will take place on Tuesday May 9 th, at theAnargyreios and Korgialenios School at 21:00. A supplement fee is required. Please
conduct the registration desk for any diary preferences.
Free afternoon
On Wednesday 9, 2023 the lectures end at 13:30 and the rest of the day is free.
GENERAL REMARKS
Refreshments
During the coffee breaks, coffee and juices will be provided free to all participants.
WiFi
Free wifi in all areas of the Anargyreios and Korgialenios School will be available.

Climate
At the beginning of May, the weather in Greece is usually dry, however on the seaside
the humidity levels are elevated. The average temperatures lie between 12-25 oC (53-77
oF). During the night, the weather is cooler but pleasant. All rooms and the lecture roomat the Anargyreios and Korgialenios School are air-conditioned.

Information for Spetses island
For more information about the Spetses island please visit
http://www.spetsesdirect.com/
https://www.secret-greece.com/spetses-island-greece/
https://spetses.gov.gr/eimai-episkeptis-5973/spetses-history/
https://www.spetses.com.gr/spetses-site/spetsesToday/history_en.php
Acknowledgments
The Organizers wish to express their most cordial thanks to Mrs. V.Zatta for her
assistance, as well as to our sponsors: ANELIS, NCSR “Demokritos”, University of Florida
and the Anargyrios and Korgialenios Scool of Spetses.

TIMETABLE CTMNM/NAGC, Spetses 8-12 May 2023
Time\Day

Monday, May 8

Tuesday, May 9

Wednesday, May 10

Thursday, May 11

Friday, May 12

8:50-9:00
Chair

WelcomeSpyros P. PerlepesGeorge Christou

Selvan DemirMark W. Meisel

Jürgen Schnack

9:00-9:30

Kasper S. PedersenDavid Britt

Boris Tsukerblat

Masahiro Yamashita

Xiaoguang Zhang

9:30-10:00

Konstantinos D. Demadis

Linda Doerrer

Sokrates T. Pantelides

Kathryn Preuss

Daniel Talham

10:00-10:30

Stephen Holmes

Shengqian Ma

Patrina Paraskevopoulou

Panayiotis Kyritsis

Nikolaos Ioannidis

10:30-10:45
10:45-11:00

Alexandros S. Armenis
Dimitris Alexandropoulos

ChristiAnna L. Brantley
Vasileios Tzitzios

Naoya Yoshikane
Efstathia Voudouri

Kleoniki Giannousi
Aizuddin Sultan

Catherine Raptopoulou
Christina Stamou

11:00-11:30

Coffee break

Coffee break

Coffee break

Coffee break

Coffee break

Chair

Andreja Jelen

Kathryn Preuss

Muralee Murugesu

Anastasios Tasiopoulos

Yannis Sanakis

11:30-12:00

Jürgen Schnack

George Froudakis

Kosmas Prassides

Mark Turnbull

Nikolia Lalioti

12:00-12:30

Yiannis Sanakis

Selvan Demir

Grace Morgan

Hai-Ping Cheng

Anastasios Tasiopoulos
Georgios Papavassiliou

12:30-13:00

José Carvalho

Jaclyn Brusso

Mario Chiesa

Vlasoula Bekiari

13:00-13:15
13:15-13:30

Francesca Adami
Zoi Lada

Vassilis Psycharis
Dimitris G. Fragkis

Michael Pissas
Alex Diodati

Miguel Gakiya-Teruya
Antonis Anastassiades

13:30-15:30

Lunch break

Lunch break

Lunch break

Lunch break

Chair

Catherine P. Raptopoulou

Stephen Hill

George Papvassiliou

15:30-16:00

Christopher W. M. Kay

Stergios Piligkos

Stephen Hill

16:00-16:30

Sotiris Christodoulou

Muralee Murugesu

Ming-Hsi Chiang

16:30-17:00

Dimitris Gournis

Catherine Dendrinou-Samara

Andreja Jelen

17:00-17:15
17:15-17:30

Konstantinos N. Pantelis
Despina Dermitzaki

Eleni Zygouri
Zahra Hooshmand

Ashlyn Hale
Eleni Hadjikyprianou

17:30-18:00
Chair

Coffee break
Talal Mallah

Coffee break
Theocharis Stamatatos

18:00-18:30

Mark W. Meisel

Yann Garcia

Talal Mallah

18:30-19:00

Wassilios Papawassiliou

Ziling (Ben) Xue

Nikolaos Tsoureas

19:00-19:15
19:15-19:30
19:30-19:45
19:45-20:00

Anastasios Keramidas
Konstantina H. Baka
Maria Chrysina

George Mitrikas
Maria Iliopoulou
Niki Mavragani

21:00 Greek Night

Free time

Coffee break
Sokrates Pantelides

Dermot Brougham
Georgia Zahariou
Konstantinos Stamatis

Sotiris Skiadas
CLOSING REMARKSProgram8:15-8:50
8:50-9:00
9:00- 9:30
9:30-10:00
10:00-10:30
10:30-10:45

10:45-11:00

11:00-11:30
11:30-12:00
12:00-12:30

12:30-13:00

13:00-13:15
13:15-13:30
13:30-15:30

15:30-16:00
16:00-16:30

16:30-17:00

17:00-17:15

17:15-17:30
17:30-18:00
18:00-18:30

Monday 8-5-2023
Registration
WelcomeChair: Spyros P. Perlepes
Kasper S. Pedersen
Magnetic Archimedean Tessellations in Coordination Solids
Konstantinos D. Demadis
The versatility of phosphonate linkers in coordination polymers
Stephen Holmes
Structure-Property Studies of Paramagnetic Group V Carbenes
Alexandros S. Armenis
High-performance DyIII Single-Molecule Magnets with D5h or D6h symmetry containing[1+1] Schiff-base macrocycles
Dimitris Alexandropoulos
High Nuclearity Homometallic 3d and Heterometallic 3d/4f clusters from the
combination Di-2-Pyridyl Ketone with selected Polyols
Coffee break
Chair: Andreja Jelen
Jürgen Schnack
Toroidal magnetic molecules stripped to their basics
Yiannis Sanakis
The magnetic properties of heterometallic clusters based on an asymmetric [Fe 3+Ln3+-Fe3+] (Ln = Gd, Tb, Dy, Ho) structural core
José Carvalho
Magnetic Resonance Experiments for the Investigation of the Electronic Structure ofYb(III)[CH(SiMe3)2]3 and Pulsed Dynamic Nuclear Polarization
Francesca Adami
Redox and Spin State Preferences in Manganese Model Complexes
Zoi Lada
Spin State Switching in Non-centrosymmetric Crystals
Lunch break
Chair: Catherine P. Raptopoulou
Christopher W. M. Kay
No End of History for Chemistry Education and Magnetic Resonance
Sotiris Christodoulou
Single Exciton Gain and Stimulated Emission in PbS CQD Films at Room
Temperature
Dimitris Gournis
Novel synthetic approaches for the development of functional 2D hybrid materials forenergy, environmental and biomedical applications
Konstantinos N. Pantelis
Deliberate replacement of trivalent metal ions in a family of pentanuclear {M III4LnIII} (M= Fe, Cr, Ga; Ln = Gd, Dy, Y) heterometallic clusters
Despina Dermitzaki
Chiral Complexes from Chiral Schiff Base Ligands: The case of {Cu 4Dy2} clusters
Coffee break
Chair: Talal Mallah
Mark W. Meisel
Materials in Metastable Forms – molecules to metals

18:30-19:00

19:00-19:30

19:30-19:45

19:45-20:00

Wassilios Papavassiliou
Investigation of the cooperative Spin-Crossover in a mononuclear manganese(III)complex via solid-state NMR crystallography
Anastasios Keramidas
Mechanism of the Reductive Activation of O2 to O22- from a Vanadium(IV) Species
and Its Potential Use in Fuel Cells
Konstantina H. Baka
Combination of highly anisotropic Dy(III) ions with diamagnetic post transition metal
ions: The case of Dy/Ga and Dy/Sn complexes
Maria Chrysina
Study of the S3 state of nature’s water-splitting catalyst by X-ray spectroscopy

Tuesday 9-5-2023
Chair: George Christou
9:00- 9:30
9:30-10:00
10:00-10:30
10:30-10:45
10:45-11:00
11:00-11:30

David Britt
Enzymatic Synthesis of the Organometallic H-Cluster of [FeFe] Hydrogenase
Linda Doerrer
An Octahedral {Mn6} Cluster Surrounded by Florinated Alkoxide Ligands
Shengqian Ma
Bioinspired Nanotrap for Nuclear Fuel Resource Mining from Ocean
ChristiAnna L. Brantley
Single-Molecule Magnets on Molecular Nanoparticles of δ-Bi2O3
Vasileios Tzitzios
Colloidal nanoparticles, liquid phase synthesis, characterization and their applications
Coffee break
Chair: Kathryn Preuss

11:30-12:00

12:00-12:30
12:30-13:00
13:00-13:15

13:15-13:30

13:30-15:30

George Froudakis
Machine Learning Algorithms for Addressing the Gas Storage Problem in
Nanoporous Materials
Selvan Demir
Employing Radicals and Bismuth in Lanthanide Single-Molecule Magnet esign
Jaclyn Brusso
Cluster-based Redox Responsive MRI Contrast Agents
Vassilis Psycharis
Structure-superstructure interrelations in non-molecular crystal structures based on
cation arrangement
Dimitris G. Fragkis
Homo- and heterometallic Mn and Mn/Ln clusters bearing pyridyl alkoxide chelateswith stereogenic centers: An approach to chiral single-molecule magnets
Lunch break
Chair: Stephen Hill

15:30-16:00
16:00-16:30
16:30-17:00
17:00-17:15

17:15-17:30
17:30-18:00
18:00-18:30
18:30-19:00

Stergios Piligkos
Molecular Lanthanide Complexes for Quantum Technologies
Muralee Murugesu
A new generation of lanthanide-based Single-Molecule Magnets
Catherine Dendrinou-Samara
Multimodal Utility of Magnetic Ferrite Nanoparticles
Eleni Zygouri
Heteroaggregation Approach for depositing Spin Crossover Nanoparticles onto Silica
Coated Gold Nanorods: A Nonlinear Optical Study
Zahra Hooshmand
New Insights in The Magnetic Anisotropy of Single-Molecule Magnets
Coffee break
Chair: Theocharis Stamatatos
Yann Garcia
Volatile Organic Compounds Sensed by Iron(II) Sensors
Ziling (Ben) Xue
Magnetism of Molecular Compounds and a Haldane MOF Revealed by Advanced
Spectroscopies

19:00-19:15

19:15-19:30

19:30-19:45

George Mitrikas
New insights into the use of encapsulated atomic hydrogen in POSS cages as spin
qubitMaria Iliopoulou
Efforts to Structurally Model the Uranyl/Vanadium Competition in Seawater Extractionof Uranium Using Amidoxime Adsorbents
Niki Mavragani
Introducing strong magnetic coupling in polynuclear Ln metallocene complexes via
the incorporation of a tetrazine radical ligand

Wednesday 10-5-2023
Chair: Selvan Demir
9:00- 9:30

9:30-10:00

10:00-10:30

10:30-10:45
10:45-11:00

11:00-11:30
11:30-12:00
12:00-12:30
12:30-13:00
13:00-13:15
13:15-13:30

Boris Tsukerblat
In Quest of Controllable Electron Transfer Aimed to
Performance Optimization of Molecular Quantum Cellular Automata
Sokrates T, Pantelides
Probing electron densities and atom-by-atom vibrational spectra by atomic-resolution
microscopy and theory reveal fascinating physics
Patrina Paraskevopoulou
Polyurea-Crosslinked Biopolymer Aerogels as a Versatile Platform for the Design and
Synthesis of Nanostructured Materials for Environmental and Biomedical Applications
Naoya Yoshikane
Coupling of structural and electronic behaviors in mixed-valence RE2.75C60
Efstathia Voudouri
Synthesis and characterisation of Spin Crossover nanoparticles of Fe(II) with 4-Amino1, 2, 4- triazole ligand
Coffee break
Chair: Muralee Murugesu
Kosmas Prassides
Spontaneous magnetoelastic effects in Prussian blue analogue molecular magnets
Grace Morgan
Spin State Switching in Crystals and Soft MatterMario Chiesa
Surface Coordination Chemistry of Single Magnetic Atoms
Michael Pissas
Crystallographic and magnetic properties of LiFeO2 and LiFe5-xMnxO8 compounds
Alex Diodati
Covalently-linked Supramolecular Dimers of {Mn2(μ-O)}2+ ComplexesThursday 11-5-2023
Chair: Mark W. Meisel
9:00- 9:30

9:30-10:00
10:00-10:30

10:30-10:45

10:45-11:00
11:00-11:30
11:30-12:00
12:00-12:30

12:30-13:00
13:00-13:15
13:15-13:30

13:30-15:30
15:30-16:00

16:00-16:30
16:30-17:00
17:00-17:15

17:15-17:30

17:30-18:00
18:00-18:30

Masahiro Yamashita
Molecular Spin Qubits for Quantum Computer and High-Density Memory Devices
Based on Molecular Magnets
Kathryn Preuss
Magnetic Ordering and SCMs from Ln(III)-radical complexes
Panayiotis Kyritsis
Zero-Field Splitting and Slow Magnetization Relaxation in Mononuclear 3d-Metal
Complexes
Konstantinos Stamatis
Chiral Schiff base Zn(II) complexes: synthesis, characterization and DNA-interaction
studies
Aizuddin Sultan
Mn3+ Spin Crossover Complexes: A Structural and Spectroscopic Study
Coffee break
Chair: Anastasios Tasiopoulos
Mark Turnbull
Low-dimensional Cu(II) magnetic lattices
Hai-Ping Cheng
First-principles study of qubit decoherence due toproton bath and qubit-qubit interactions
Vlasoula Bekiari
TiO2-based nanocatalysts for steroid hormones degradation in water
Miguel Gakiya-Teruya
Molecular Spin Qubits Based on High-Symmetry Lanthanide Complexes
Antonis Anastassiades
Rare Nuclearities and Unprecedented Structural Motifs in Manganese Cluster
Chemistry from the Combined Use of Pyridyl and Non-Pyridyl Alcohols
Lunch break
Chair: George Papvassiliou
Stephen Hill
Application of wideband pulsed high-frequency EPR to molecular quantum spinscience
Ming-Hsi Chiang
Oxygen-Stable Inhibited State of [FeFe] Hydrogenase
Andreja Jelen
Nanostructure-driven magnetic phenomena in transition-metals high-entropy alloys
Ashlyn Hale
Molecular Analogues of the Structure and Spin Vector Ordering of LnMnO3
Manganite Perovskites
Eleni Hadjikyprianou
Catalysis of a Diels-Alder Reaction Between Azachalcones and Cyclopentadiene by
a Recyclable Copper(II) Metal-Organic Framework
Coffee break
Chair: Sokrates Pantelides
Talal Mallah
Electron delocalisation in switchable polynuclear Ni3 and Ni6 complexes based on atriphenylene trisemiquinone bridge

18:30-19:00
19:00-19:30

19:30-19:45

19:45-20:00

Nikolaos Tsoureas
η6-phenoxide 1st row transition metal complexes in unusual geometries
Dermot Brougham
Insights into magnetic ordering and routes towards application for iron-oxide
nanoparticle suspensions from combined colloidal analysis, NMR relaxometry andAC-field hyperthermia
Georgia Zahariou
Possible role of the Tyrosine Z in the S2 to S3 transition of the Oxygen Evolving
Complex of Photosystem II
Kleoniki Giannousi
Self-Therapeutic Nanostructures: The case of Zn-based Nanoparticles
Friday 12-5-2023
Chair: Jürgen Schnack

9:00- 9:30

9:30-10:00

10:00-10:30
10:30-10:45

10:45-11:00

11:00-11:30
11:30-12:00

12:00-12:30

12:30-13:00

13:00-13:15

13:15-13:30

Xiaoguang Zhang
First Principles Calculations of Near-Resonance Raman Intensity as Sensitive Toolfor 2D Materials and Magnetic Molecules
Daniel Talham
How Interfaces Influence Phase Transformations in Layered Magnets, Hybrid
Perovskites and Related Materials
Nikolaos Ioannidis
The S3 state of the oxygen evolving complex of spinach Photosystem II.
Catherine Raptopoulou
Heterometallic Cu/Ln complexes based on cubane subunits: synthesis, molecularand intermolecular structure, and magnetic characterization .
Christina Stamou
Aspects of the Coordination Chemistry of Benzotriazoles: Silver(I) Complexes with
Antibacterial Properties and Reactivity of Copper(II) Clusters
Coffee break
Chair: Yannis Sanakis
Nikolia Lalioti
Observation of Two-Step Spin Transition in Iron(II) 4-amino-1,2,4-triazole Based Spin
Crossover Nanoparticles
Anastasios Tasiopoulos
Fine Tuning the Hydrophobicity of a New Cu 2+ 3-Dimensional MOF Through Single Crystal Coordinating Ligand Exchange Transformations
Georgios Papavassiliou
Molecular ordering of nanoconfined ionic liquids detected with T 2-resolved diffusion
NMR
Sotiris Skiadas
On the Way to Mixed-metal Cu(II/Fe(III) Coordination Clusters Using 2-Pyridoximato
Ligands
Closing Remarks

ABSTRACTSHigh Nuclearity Homometallic 3d and Heterometallic 3d/4f clusters
from the combination Di-2-Pyridyl Ketone with selected Polyols
D. I. Alexandropoulos,a,* K. Skordi,a A. Fournet,b G. Christou,b A. J. Tasiopoulosa
a. Department of Chemistry, University of Cyprus, Nicosia 1678, Cyprus
b. Department of Chemistry, University of Florida, Gainesville, Florida 32611, USA
Emails: alexandropoulos.dimitris@ucy.ac.cy (presenting author)
atasio@ucy.ac.cy (corresponding author)
Polynuclear coordination complexes of paramagnetic metal ions have become the focus ofintense investigation over the last few decades since they often possess interesting physicalproperties and fascinating structural features.
A crucial parameter in the design of coordination complexes is the choice of the organic ligand
because the latter dictates the structure, the topology and, therefore, the properties of theresulting compounds. One of the ligands that have been successfully employed in metal cluster
chemistry is di-2-pyridyl ketone ((py)2CO), which has a fruitful coordination chemistry.[1] Our group
recently reported new high nuclearity [Mn 23] and [Mn24] compounds as well as a series of Mn/4f
complexes that were prepared from the combination of ((py)2CO) with polyols.[2] Herein, we reportan extension of these investigations that involve the synthesis of a series of homometallic andheterometallic complexes from this ligand combination approach (Figure 1). The reported
compounds possess rare nuclearities and unprecedented structural motifs as well as interesting
magnetic properties.

Figure 1: Molecular structure of a representative compound discussed in this work. Color scheme: Mn II,
cyan; MnIII, blue; O, red; N, green; C, black. Hydrogen atoms are omitted for clarity.

References[1] A. J. Tasiopoulos and S. P. Perlepes, Dalton Transactions, 2008, 41, 5537-5555.
[2] K. Skordi, A. Anastassiades, A. D. Fournet, R. Kumar, M. Schulze, W. Wernsdorfer, G.
Christou, V. Nastopoulos, S. P. Perlepes, C. Papatriantafyllopoulou and A. J. Tasiopoulos, Chem.
Comm., 2021, 57, 12484-12487.
Acknowledgments
This work was supported by the Cyprus Research and Innovation Foundation Research Grant“EXCELLENCE/0421/399” which is co-funded by the Republic of Cyprus and the European
Regional Development Fund.

Rare Nuclearities and Unprecedented Structural Motifs in Manganese
Cluster Chemistry from the Combined Use of Pyridyl and Non-Pyridyl
Alcohols
A. Anastassiades,a,* D. I. Alexandropoulos,a A. Hale,b G. Christou,b A. J. Tasiopoulosaa.

Department of Chemistry, University of Cyprus, Nicosia 1678, Cyprus
b. Department of Chemistry, University of Florida, Gainesville, Florida 32611, USA
Emails: anastassiades.antonis@ucy.ac.cy (presenting author)
atasio@ucy.ac.cy (corresponding author)

Polynuclear manganese clusters have been of great interest due to the ability of Mn ions to
adopt a variety of oxidation states (ie. II, III, and IV) and form high nuclearity metal-oxo clusters
that can find applications in different research fields including bioinorganic chemistry, materials
science, and molecular magnetism. In the latter case Mn clusters hold a special place, since, they
can act as high spin molecules and/or Single-Molecule Magnets (SMMs).[1]Our group has had a continuing interest in the synthesis of polynuclear Mn complexes withnovel structural characteristics and we have employed several polyol-type chelating/bridging
groups as primary organic ligands or combinations of them, following a mixed ligand approach.
Herein, we report the synthesis, structural and magnetic characterization of the complexes
deriving from the combined use of 2-(pyridin-2-yl)propane-1,3-diol (pypdH2) ligand and various
pyridyl and non-pyridyl alcohols (Figure 1). In addition, the compounds obtained from the use of
a combination of di-2-pyridyl ketone ((py)2CO) and diethanolamine (deaH2) in homometallic Mn
and heterometallic Mn/Ln chemistry will also be discussed.

Figure 1: Molecular structure of a representative compound discussed in this work. Color scheme: Mn II,
cyan; MnIII, blue; O, red; N, green; C, black. Hydrogen atoms are omitted for clarity.

References[1] R. Bagai; G. Christou, Chem. Soc. Rev. 2009, 38, 1011-1026.
Acknowledgements
This work was supported by the Cyprus Research and Innovation Foundation Research Grant“EXCELLENCE/0421/399” which is co-funded by the Republic of Cyprus and the European
Regional Development Fund.

High-performance DyIII Single-Molecule Magnets with D5h or D6hsymmetry containing [1+1] Schiff-base macrocycles
A. S. Armenis,a,* G. P. Bakali,a D. I. Alexandropoulos,b Th. C. Stamatatosaa.

Department of Chemistry, University of Patras, Patras 26504, Greeceb. Department of Chemistry, University of Cyprus, 1678 Nicosia, Cyprus
Emails: alexarmenis1996@gmail.com (presenting author)
thstama@upatras.gr (corresponding author)

The search for new molecules exhibiting slow relaxation of magnetization under a plausible
blocking temperature is currently one of the most appealing research topics in the interdisciplinary
fields of inorganic and coordination chemistry, materials science, physics, and theoreticalchemistry. Lanthanide(III) ions play a pivotal role in the quest for efficient single-molecule magnets
with potential applications in memory storage, molecular spintronics, and quantum computation.
This is mainly due to the large magnetic anisotropy that most 4f-metal ions possess, which arises
from the strong spin-orbit coupling and the crystal-field effects from the coordinated ligands.[1]Seeking for new synthetic strategies towards the preparation of single-molecule magnets(SMMs) with large energy barriers for the thermally-assisted relaxation of magnetization, the focus
of our research is placed around mononuclear DyIII complexes with designed ligands suitable toyield the targeted coordination geometries (D5h, D6h) and subsequently reducing the efficiency of
the through-barrier relaxation pathways.[2] Herein, we report the synthesis, structural andmagnetic characterization of a new family of mononuclear, air-stable DyIII SMMs, by employing
the macrocyclic effect and successfully promoting an N5, N3O3, and N4O2 equatorial ligation
around a single DyIII ion resulting from a [1+1] metal-assisted condensation reaction (Figure 1).
As a result, we have been able to chemically engineer new coordination compounds withpentagonal or hexagonal bipyramidal geometries, bearing strongly bound axial ligands andexhibiting SMM behaviors with large Ueff values.

Figure 1: Molecular structures and ac magnetic dynamics of representative complexes discussed in thiswork. Color scheme: Dy=yellow; O=red; N=blue; C=grey. Hydrogen atoms are omitted for clarity.

References:[1] L. Bogani and W. Wernsdorfer, Nat. Mater., 2008, 7, 179.
[2] J. Tang et al. ACS Materials Lett., 2022, 4, 307−319.

Combination of highly anisotropic Dy(III) ions with diamagnetic posttransition metal ions: The case of Dy/Ga and Dy/Sn complexes
K. H. Baka,* Th. C. Stamatatos
Chemistry Department, University of Patras, Patras 26504, Greece
Emails: mpakakonstantina645@gmail.com (presenting author),
thstama@upatras.gr (corresponding author)
The combination of paramagnetic 3d- and 4f-metal ions to create single-molecule magnets(SMMs) has attracted extensive attention over the past few decades. However, it has become
clear that the relatively weak 3d-4f exchange coupling contributes to lower energy barriers for themagnetization reversal (Ueff) when compared to the homometallic 4f-based SMMs. Lately, it has
been observed that the use of diamagnetic metal ions in combination with anisotropic andparamagnetic ones can increase the Ueff values, with a few examples -using the closed shell
Zn(II)- being reported.[1] To this end, an alternative and very appealing route is the choice of
diamagnetic metal ions, such as the triel Ga(III), which can play the role of magnetic dilutor,
desirably leading to improved magnetic properties and also having flexible coordinationgeometries, as exemplified by tetrahedral, trigonal-bipyramidal, and octahedral geometries, thus
leading to new structural motifs of molecular clusters with unprecedented topologies. The heavier
element, which has diagonal relationship with Ga and exhibits similar properties, is Sn. The
analogous chemistry of 4f-metal ions with the tetrel Sn(II/IV), has not been systematically
explored, although Sn(II/IV) has a large spin-orbit coupling and it could -in principle- contribute to
the enhancement of the molecular magnetic anisotropy.[2] Herein, we report the self-assembly
synthesis and characterization of two new heterometallic p/4f clusters, namely {Ga III7DyIII4} and{SnII4DyIII8} (Figure 1), bearing the ligand α-benzoin oxime.

Sn2+{SnII4DyIII8}+

Dy3+{GaIII7DyIII4}

Ga3+

Figure 1. (left) The molecular structures of the {GaIII7DyIII4} (right) and {SnII4DyIII8} clusters, and (center)the chemical formula of the employed ligand α-benzoin oxime.

[1] S. Titos-Padilla, J. Ruiz, J. M. Herrera, E. K. Brechin, W. Wersndorfer, F. Lloret, E. Colacio,
Inorg. Chem., 2013, 52, 9620−9626.
[2] S. C. Coste, B. Vlaisavljevich, D. E. Freedman, Inorg. Chem., 2017, 56, 8195−8202

TiO2-based nanocatalysts for steroid hormones degradation in water
V. Bekiari1,* L. Grigorakou1,2, C. Christophoridis2,3, K. Fytianos2
1

Department of Agriculture, University of Patras, Messolonghi 30200, Greece
Environmental Pollution Control Laboratory, Chemistry Department, Aristotle Universityof Thessaloniki, 54124 Thessaloniki, Greece
3
Institute of Nanoscience & Nanotechnology, NCSR Demokritos, Patr. Gregoriou E & 27
Neapoleos Str, Agia Paraskevi, 15341, Greece
2

Email: bbekiari@upatras.gr
During the last years, an increasing number of pharmaceuticals such as antibiotics, hormones,anti-parasitics, anti-depressants, and anti-cancer drugs have been found to impact with high risk
the natural environment worldwide. Although the individual substances are present in small
amounts in the environment (micropollutants), their mixtures can have a significant environmental
effect. Medicinal substances and their metabolites are found in wastewater and rivers acrossEurope, highlighting the need for effective wastewater treatment methods. While modern methods
such as infrared treatment and advanced oxidation processes can reduce pharmaceuticalresidues significantly, pollution remains inevitable due to the nature of these substances. Steroid
hormones are among the most common studied pharmaceuticals due to their widespread use
and their serious effects on environmental quality and human health. The common sources ofthese hormones in environment are human and livestock excretion, medicines and agricultural
wastes. The present work aims to investigate the removal of two hormones, namely Progesterone
and Drospirenone, under photocatalytic transformation with titanium dioxide (TiO 2) films. The
degradation of the hormones by photocatalysis was studied with respect to pH, catalysis time,
and the amount of the used catalyst. The results showed that the removal rate exceeded 90%.
Additionally, results on the regeneration and reuse of the catalyst are presented.

Figure. Effect of the photocatalysis time on the % removal of Progesterone at three different
pH=3, 6, 8 experimental conditions. (ΤiΟ2: 1.5 g/200 mL, CProg=5 mg/L).
[1]
D. Panagiotaras, V. Bekiari, E. Stathatos, D. Papoulis, G. Panagopoulos, A.N. Kalarakis,
I. Iliopoulos, E. Kourkouta and P. Mavrokota, ‘Use of halloysite–TiO2 nanocomposites for thedecomposition of tebuconazole’, Desalination and Water treatment, 2018, 127, 132.
[2]
B.Almazrouei, D. Islayem, F. Alskafi, M.K. Catacutan, R. Amna, S. Nasrat, Banu Siziri, I.
Yildiz, Emerging Contaminants, 2023, 9, 100210.

Single-Molecule Magnets on Molecular Nanoparticles of δ-Bi2O3
ChristiAnna L. Brantley,*a Elly Daniels,a Michael Schulzeb,c, Khalil A. Abboud,a Wolfgang
Wernsdorferb,c, and George ChristouaaDepartment of Chemistry, University of Florida, Gainesville, FL 32611, USAb

Karlsruher Institut für Technologie (KIT), Physikalisches Institut, Wolfgang-Gaede-Str. 1, 76131
Karlsruhe, GermanycInstitute of Quantum Materials and Technologies (IQMT), Hermann-von-Helmholtz-Platz 1,
Gebäude 640, 76344 Eggenstein-Leopoldshafen, Germany

Email: brantley.c@ufl.edu

Molecular chemistry brings powerful advantages to the study of nanoscale materials ofdifferent kinds, and in recent years research in this area has been rapidly growing. In the field of
molecular nanomagnetism these advantages have been crucial in the study and understandingof single-molecule magnets (SMMs) and have led to the discovery of new quantum physics
phenomena important to 21st century technologies. More recently, our group has utilized amolecular bottom-up approach to attain a versatile and growing library of truly monodispersed(single-sized) metal-oxo clusters with the same structure as the corresponding bulk oxides, which
we call ‘molecular metal-oxide nanoparticles’ (MNP’s). MNP’s possess a monolayer shell oforganic ligands, imparting solubility and crystallinity and allowing structural characterization toatomic resolution by single-crystal X-ray crystallography. The synthesis of MNPs in the ultra-small
size regime is important to understanding the size-dependent properties generally exhibited bynanoparticles. Our efforts began in cerium dioxide (CeO 2) chemistry, which is important for avariety of applications in industrial, environmental, and bio-medical catalysis. To date, our grouphas synthesized the largest Ce/O MNP, with a nuclearity of 100, exhibiting the fluorite structureof CeO2. Since then our efforts have been extended to bismuth(III), iron(III), and Mn(III,IV) oxides,
and also mixed-metal oxides. Specifically, Bi/O- based materials are interesting as bismuth is a
non-toxic heavy metal that has been investigated in materials for multiferroics, photocatalysts,
and electrolytes for fuel cells. Bismuth trioxide (Bi2O3) is a semiconducting material relevant tophotocatalysis and solid oxide fuel cells. Recently, we have begun investigating MNPs withmagnetic units on their surface as molecular analogues of magnetic units on surfaces. This allows
the binding of the SMM to the surface and any magnetic interactions between the SMM units to
be determined.The syntheses, structures, and magnetic properties of SMMs bound to MNPs of
δ-Bi2O3 will be described.

Enzymatic Synthesis of the Organometallic H-Cluster of[FeFe] Hydrogenase
R. David Britt
Department of Chemistry, University of California, Davis: Davis CA 94616
Email: rdbritt@ucdavis.edu
Scheme of enzymatic and semisynthesis of the H-cluster(1)
Synthesis
Assisted

Tyrosine,
SAM,
Fe2+
CysteineII

Complex B carrier, synB

(2)
I

I

syn-dimer

(3)
I

I

adt-dimer“H-cluster”
HydG
Enzyme

HydE

HydF
I

I

.

Figure 2: Enzymatic synthesis of the [FeFe] hydrogenase H-cluster (lower track) along with synthetic clusters (1-3) used to
The bypass[FeFe]one,hydrogenase
enzymes
are well suited to H 2 formation, producing up to 10000 H 2alternatively
two, or all threematurases.
molecules per second, and have therefore generated much interest •for renewable energy
C5’ of adenosine.
the majority
rSAM enzymes,
includingthis 5’dAdo abstracts a speciﬁc H-atom
applications.In The
H-clusterofconsistsof a binuclear[2Fe]HydG,
H subcluster which is linked via a bridging
from the enzyme’s substrate to generate a substrate-centered radical and dAdoH. In the case of HydG, the subcysteine to a [4Fe-4S]H cluster. This [2Fe]H subcluster contains the organometallic elements ofstrate is tyrosine, and this radical chemistry drives its fragmentationand leads in some fashion to the Fe-boundthe H-cluster: the two irons each have a CO and a CN- terminal ligand and are bridged by a third
CN and CO ligands of the H-cluster, with different models as to how the latter chemistryoccurs.
+andfreea unique
SCH
2NHCH2S azadithiolate (adt) moiety. The H and H2 substrates are
We CO
use cell
synthesis
to assemble
the H-cluster within [FeFe] hydrogenase HydA1 protein using individproposedHydE,
to bindto andthis [2Fe]along
In addition
relative
rarityof enzymes
H unit.
ually expressed
HydF,
and react
HydGatmaturaseswitha cocktailtoofthe
requiredsmallmolecules
and some
carrying
outorganometallic
reactions,biosynthesisoftheH-cluster
poisessomespecificlysate from the E. coli expression. (19) Combined with CW EPR and high resolution pulse EPR methods, thischallenges.
Of course,
free ofCO
CN - molecules
In addition,
the bridging
adt moiety
allows one
to determine
the source
theandindividual
atoms ofare
thetoxic.
H-cluster,
as measured
in the various
paramagnetic H-cluster
forms
such
as Hox ,inHsolution.
CO,
and
H
.
(20–23)
This
in
turn
guidesexperiments
targetingindividual
is known
to beunstableThe
H-cluster
biosynthesisisperformed
by
a
set
of
three
ox
hyd
maturase
enzymes,proteins,
allowingHydE,
signiﬁcantprogressin mappingout the biosynthesisof theoverview“maturase”
HydF,
and HydG,
each containing
Fe-S clusters.
TwoH-cluster.
of these,An
HydE
of our resultsispresented
in
Fig.
2.
(24,
25)
and HydG, are members of the radical SAM superfamily of enzymes, while HydF is a GTPase.
In ourmodel
the H-clustersynthesisa begins
HydG, a radical
SAM
containing
twoincludes
Fe-S clusters.
Our
approach
to developing
viable withmechanistic
proposalforenzyme
H-clustersynthesis
One is chemical
a “standard”
radical
SAM [4Fe-4S]
cluster,butsynthesis,
an X-ray crystal
subsequentsuch
biochemistry
biologytechniquessuch ascell freeisotopestucturesensitiveand
spectroscopy
asrevealed the presence of an additional [4Fe-4S] cluster bridged to a ﬁfth “dangler Fe” via the sulfur of a chelated
electron paramagnetic resonance, and the use of synthetic clusters that can serve as functional
cysteine. (26,27) The two FeS clusters are connected by a ⇡ 24Å TIM barrel channel. The radical SAM chemistry
substitutes for enzyme intermediates.
lyses the substrate, L-tyrosine, (28) initially forming p-cresol and dehydroglycine (DHG). The DHG is further
fragmented to form CO and CN− , a process we have modeled with QM/MM methods as occurring through aradical cascade. (29) The CO and CN− bind at a the dangler Fe at the other end of the TIM barrel. After a second
tyrosine lysis a second CO binds to the dangler Fe, and the second CN− replaces the bridging cysteine S ligand
to the auxiliary [Fe-4S] cluster, releasing the product of HydG, a [Fe(II)(CN)(CO)2(cysteinate)]− organometallic
mononuclear Fe species which serves as the substrate to a second rSAM enzyme, HydE. (27) This mechanistic
model, based largely on isotope-sensitive spectroscopy (EPR and FTIR), was conﬁrmed in a semisynthesis study
in collaboration with the Tom Rauchfuss laboratory, (30) in which Rauchfuss and coworkers synthesized a carrierof our proposed HydG product, termed SynB (1) (Fig. 2). This synthetic species allows complete activationof hydrogenase in the cell free synthesis with HydG deleted, which otherwise gives zero activity. EXAFS of theassembled cluster using SynB made alternatively with cysteine and selenocysteine showed that the bridging S/Seof the [2Fe]H subcluster are sourced from this SynB S/Se. (30) The remaining atoms with unknown molecularorigin were the CH2NHCH2 of the azadithiolate bridge, then showed by pulse EPR to originate from the 3C andInsights into magnetic ordering and routes towards
application for iron-oxide nanoparticle suspensions from combined
colloidal analysis, NMR relaxometry and AC-field hyperthermia
D. Brougham,* K. Nigoghossian, S. Shingte. E. McKiernan, J. Wychowaniec, E. Aluri
School of Chemistry, University College Dublin, Ireland
Email: dermot.brougham@ucd.ie

In recent years the development of magnetic iron-oxide nanoparticles (MNPs) forbiomedical applications, both as suspensions and as components in nanocomposites, hasprogressed. A particular focus is on preparing materials with multiple responses, typically any two
from MRI image contrast generation, AC-field induced local heating (hyperthermia) andmagnetophoretic capture. In this talk I will describe the field and will show some recent work fromour laboratory on the synthesis, surface modification, colloidal stabilization and in vivo fate of
MNPs. [1] The application of fast-field cycling NMR relaxometry to study magnetic ordering, using
the 1H nuclei as a spy, of the intact hydrated materials in situ has been key to understanding how
moment dynamics determines hyperthemic and MRI responses. [2, 3] I will describe how this iscan be done for magnetic nanosphere, nanocube and nanoflower suspensions, and timepermitting for magnetic hydrogels. [4][1] E. P. McKiernan, C. Moloney, T. Roy Chaudhuri, S, Clerkin, K. Behan, R. M. Straubinger, J.
Crean, D. F. Brougham. Acta Biomaterialia, 2022, 152, 393-405.
[2] E. MacMahon, D. F. Brougham. Langmuir, 2023, 39 2171-2181.
[3] S. Shingte, A. Phakatkar, E. McKiernan, K. Nigoghossian, S. Ferguson, R. ShahbazianYassar, D. F. Brougham. Chemistry of Materials, 2022, 34, 10801-10810.
[4] P. Monks, J. K. Wychowaniec, E. McKiernan, S. Clerkin, J. Crean, B. J. Rodriguez, E. G.
Reynaud, A. Heise, D. F. Brougham. Small, 2021, 17, 2004452.

Cluster-based Redox Responsive MRI Contrast Agents
J. L. Brusso*
Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ontario, Canada
Email: jbrusso@uottawa.ca

Transition metal molecular clusters hold great promise as MRI probes, where carefulselection of chemical design elements can afford control over the size, shape and total spin stateof the contrast agent molecule. A key characteristic of transition metal molecular clusters that canendow these contrast agents with advanced in situ reactivity to biomolecular changes in theirenvironment is that the collection of metal ions within the cluster are linked electronically and can
act as a single entity. To date, the potential of transition metal molecular clusters as MRI contrast
agents have not been realized due to the problem of cluster dissociation/speciation in biologicalmedia.
To resolve this challenge, we have employed the N-2-pyrimidylimidoyl-2-pyrimidylamidine
chelate to selectively bind 3d metal ions to form highly stable mixed metal clusters. This
presentation will focus on these biologically stable chelates, in which the microenvironmentresponsive chemical activities of our mixed metal clusters enable us to map biochemical redox
potentials spanning reducing and oxidizing environments. Through spectroscopic,
electrochemical and magnetic analysis along with in vitro and in vivo studies, the application ofiron and manganese homo- and heterometallic triskelion-shaped metal clusters as MRI contrast
agents capable of mapping tumor redox status through a simple T 1w/T2w ratiometric approach
will be demonstrated. The contrast agent design strategy presented introduces heteropolynuclear
transition metal complexes suitable for semi-quantitative in vivo MR imaging of tissue redox status
and opens up new avenues for non-invasive characterization of biochemical microenvironments
by MRI.

Figure. Molecular structures (top) and colour-coded mapping of tumor xenograft redox status (bottom) for
FeMn3 (left) and MnMn3 (right).

Magnetic Resonance Experiments for the Investigation of theElectronic Structure of Yb(III)[CH(SiMe3)2]3 and Pulsed Dynamic
Nuclear Polarization
José P. Carvalho*1, Nino Wili1, Anders B. Nielsen1, Niels Chr. Nielsen1, Andrew J. Pell2,
Christophe Copéret3, Gunnar Jeschke3, Guido Pintacuda2
1

Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus
University, Gustav Wieds Vej 14, DK-8000 Aarhus C, Denmark.
2
Université Lyon, ENS Lyon, Université Lyon 1, CNRS, High-Field NMR Center of Lyon,
FRE 2034, F-69100 VILLEURBANNE, France
3
Department of Chemistry and Applied Biosciences, ETH Zurich, Wolfgang-Pauli-Strasse
1-5, 8093 Zurich, Switzerland
Email: jose.carvalho@inano.au.dk
Obtaining high-quality NMR data is quite challenging in many chemically relevant systems.
Some of the main limitations are poor sensitivity, large anisotropic interactions and fast relaxation
times. Nevertheless, in order to obtain insight into the bonding and electronic structure, NMR is
still an invaluable tool, hence the importance of new and improved techniques for both acquisition
and interpretation of NMR data. In this context, this talk will first focus on the study of theparamagnetic Yb(III) alkyl complex Yb(III)[CH(SiMe 3)2]3 [1], where a combination of lowtemperature X-ray diffraction and state-of-the-art solid-state NMR and EPR methods, assistedwith quantum chemical calculations, permitted the characterization of its geometry and electronic
structure. Lastly, this talk will focus on pulsed Dynamic Nuclear Polarization, where a sequenceof microwave pulses induces the transfer of polarization from unpaired electrons to thesurrounding nuclei [2], by showing a new broadband modulated sequence with increased
electron-offset compensation.

[1] Ashuiev, A., Allouche, F., Carvalho, J. P., Sanders, K. J., Conley, M. P., Klose, D., Lapadula,G., Wörle, M., Baabe, D., Walter, M. D., Pell, A. J., Copéret, C., Jeschke, G., Pintacuda, G.,
Andersen, R. A. (2023). Electronic structure of Yb (III)[CH(SiMe 3)2]3 from magnetic resonancespectroscopies[2] Wili, N., Nielsen, A. B., Völker, L. A., Schreder, L., Nielsen, N. C., Jeschke, G., Tan, K. O.
(2022). Designing broadband pulsed dynamic nuclear polarization sequences in static solids.
Science Advances, 8(28), eabq0536

First-principles study of qubit decoherence due toproton bath and qubit-qubit interactions
Hai-Ping Cheng*, Xiao Chen, Haechan Park, Silas Hoffman, and James N. Fry
Department of Physics and the Quantum Theory Project
University of Florida, Gainesville FL 32611, USA
Email: hping@ufl.edu
We study spin decoherence due to coupling with a surrounding nuclear spin bath of anelectronic molecular spin of a vanadyl phthalocyanine (VOPc) molecule integrated on anarmchair-edged graphene nanoribbon (GNR). Density functional theory (DFT) is used to obtainground state atomic configurations. Decay of spin coherence in Hahn echo experiments is thensimulated using the cluster correlation expansion method with a spin Hamiltonian involving
hyperfine and electric field gradient tensors calculated from DFT. We find that the decoherencetime T2 is anisotropic with respect to magnetic field orientation and determined only by the protons
both on VOPc and GNR. Large electron spin echo envelope modulation (ESEEM) due to Nitrogen
and Vanadium nuclear spins were present at specific field ranges where nuclear Zeeman
energies is in near resonance with hyperfine interaction. We also examine, at the clock transition,a S = 1 qubit coupled to many other spins by changing the magnitude of the dipole interaction
between the qubit and other central spins. This simulation is inspired by recent work on amolecular magnetic crystal [1].

Figure: VOPc in a quasi-1D configuration[1] Electron-nuclear decoupling at a spin clock transition, K. Kundu, J. Chen, S. Hoffman, J.
Marbey, D. Komijani, Y. Duan, A. Gaita-Arino, J. Stanton, Xg. Zhang, H.-P. Cheng, and S. Hill
Communications Physics Vol. 6, Article number: 38 (2023)

Oxygen-Stable Inhibited State of [FeFe] Hydrogenase
Ming-Hsi Chiang
Institute of Chemistry, Academia Sinica,Nankang, Taipei 115, Taiwan
Email: chiangmh@gate.sinica.edu.tw[FeFe] hydrogenases display catalytic H 2-evolution and oxidation ability, which offers an
opportunity for the implementation to applications of H 2-production devices and fuel cells. One
drawback of [FeFe] hydrogenases is its oxygen sensitivity toward degradation of the active site.
It is found that the vacant site at the Fed center (the Fe distal to the attached [4Fe4S] subset),
which is open to substrate binding, is susceptible to the coordination of molecular oxygen. It leads
to the formation of a transient superoxide/peroxide species, resulting in the degradation of the Hcluster. Recent discoveries suggest that the presence of the H inact state of the H-cluster mitigates
the influence of O2 attack. In the O2-resistant Hinact state, the terminal apical site of the Fe d isblocked by an exogenous sulfide (SH–) or a cysteine residue (C367) of the peptide loop in theproximity of the Fed. We herein report the inhibitor-bound 2Fe2S model complexes with biologicalrelevance to the Hinact state. The complexes are characterized to compose of the terminal Cl- (orSH-) ligation to the Fe center with the inverted geometry bearing the bridging CO group. The t-X(X = Cl, SH) coordination, revealing the terminal inhibitor-binding behavior, is labile and kineticallycontrolled. The t-SH ligation is weaker than the t-Cl analog, and is easily replaced by exogenous
Cl– salts for the formation of the more stable t-Cl species. The Fe2 core displays 2 fully oxidized
Fe(II) centers, consistent with the results of the biochemical study. Both inhibitor-bound species
are resistant to O2 coordination and decomposition. The catalytic activity investigation involving
halides might have suggested the other candidate to the oxygen-tolerant, catalytic inactivatedstate.

Surface Coordination Chemistry of Single Magnetic Atoms
Mario Chiesa
Department of Chemistry and NIS Centre of Excellence, University of Turin, via Giuria 9, 10125
Torino, Italy.
Email: mario.chiesa@unito.it
Abstract“Adsorbed, chemisorbed, embedded, anchored, grafted” are all different words used to describe thevariety of bonding interactions of an atom with the surface of a support. Single metal atoms on surfaces
provide novel catalytic, optical, electronic, or magnetic properties, which - just as in classical coordination
chemistry - will depend on the degree of overlap and energy difference of the interacting orbitals. Oxides
are of key technological importance in different areas including advanced functional materials, solid statechemistry and catalysis and magnetic atoms or ions stabilized on their surfaces provide platforms tounderstand and tune chemical and physical properties for a range of applications. Key to all this is thenature of the metal-oxygen bond and the spectroscopic study of oxygen is of fundamental importance toelucidate the complex interfacial coordination chemistry of single magnetic atoms or ions on oxidesurfaces. EPR and its related hyperfine techniques offer a unique opportunity to explore and understandthe nature of the chemical bonding in metal-oxide systems through the detection of the 17O hyperfine
interaction. In this talk I will give an overview of experimental considerations and relevant examples
specific to 17O hyperfine spectroscopy of single isolated magnetic atoms in zeolites emphasizing theconnection between interfacial and molecular inorganic coordination chemistry and implications forreactivity and the engineering of long-living spin systems.

Figure 1. Calculated SOMO Orbitals and qualitative orbital energy splitting diagrams for the
single magnetic atoms presented in this talk. Colour code: red O, green Si, mauve Al.

[1] E. Salvadori, P. C. Bruzzese, E. Giamello, M. Chiesa, Acc. Chem. Res. 2022, 55, 3706.
[2] Y. L. Liao, P. Bruzzese, E. Salvadori, M. Chiesa JMRO 2023, 100101.

Sinlge Exciton Gain and Stimulated Emission in PbS CQD Films at Room Temperature
S. Christodoulou1,* M. Stylianou1, N. Taghipour2, G. Konstantatos2, A. Othonos3
1

Inorganic Nanocrystals Laboratory, Department of Chemistry, University of Cyprus, Nicosia,
1678 Cyprus
2
ICFO, Institut de Ciències Fotòniques, The Barcelona Institute of Science and Technology,
Castelldefels, Barcelona, 08860 Spain
3
Laboratory of Ultrafast Science, Department of Physics, University of Cyprus, Nicosia, 1678
CyprusEmail: christodoulou.sotirios@ucy.ac.cy
The last two decades CQD technology has delivered ultra-low lasing and stimulated emission
thresholds even with continuous wave excitation (CW). Nevertheless, the research has centred
in UV-Vis while very few examples has been shown in the low energy part of the electromagnetic
spectrum. On the other hand, light sources (lasers) in NIR is still the last piece missing for therealization of silicon Photonics (CMOS), while photodetectors and modulators on Si have been
already demonstrated. Apart from silicon photonics, the realization of low-cost, solutionprocessed materials with gain across the telecommunication window is of paramount importancefor expanding the optical fiber data capacity beyond the limit of currently used Er-doped amplifiers.
The realization of low-threshold and high gain amplified spontaneous emission (ASE) with highdegree of tunability across the telecom band has not been achieved yet. The reason behind thischallenge has been the high degeneracy of states in infrared CQDs (eight-fold degeneracy for
PbS-chalcogenides).
To tackle the high degeneracy of the PbS CQD we developed a doping scheme, which allow
us heavily dope the PbS CQD filling with electron the conduction band 1. Moreover, on the way tosuppress the Auger recombination we studied core/shell structures with PbSe and CdS as ashelling material. Hence, transient absorption of both PbS/PbSe 2 and PbS/CdS CQDs showed
long Auger lifetimes up to 350 ps and high gain values. In line with the TA results, ASE
measurements shows single exciton stimulated emission in CQD films at room temperatures. The
stimulated emission wavelength ranges from 1500 – 1650 nm covering the whole telecom bands,
while the FWHM is as narrow as 14meV. Therefore, we demonstrate nearly full coverage intelecom wavelengths with stable conductive CQD films, combined with high gain and single
exciton threshold paving the way for the realization electrically pumped laser.

Figure. PbS CQDs doping scheme and collective ASE spectra from a series of PbS CQD films
show the tunability of the ASE peak from 1530 to 1650 nm, within the range of the fiber-optic
communication bands.
[1] S. Christodoulou et.al. Nano Lett. 2020, 20, 8, 5909–5915[2] N. Taghipour et al. Adv.Mater.2023, 35, 2207678

Study of the S3 state of nature’s water-splitting catalyst
by X-ray spectroscopy
Maria Chrysina

Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, Athens, Greece
Email: m.chrysina@inn.demokritos.gr

Water splitting in photosynthetic organisms occurs at the Mn4Ca cluster, embedded in theprotein scaffold of Photosystem II. The Mn 4Ca cluster cycles through a progression of oxidised
states (S0→S1→S2→S3→S0). Dioxygen is formed and released during the last S 3→S0 transition.
Commonly accepted formal oxidation states of the four Mn ions in the S 0, S1, and S2 states are
MnIII3MnIV, MnIII2MnIV2, and MnIIIMnIV3, respectively. However, controversy remains regarding theformal oxidation state and electronic structure of the S3.
X-ray absorption and emission spectroscopy probe selectively an element, in the present
case, Mn and gives information regarding the oxidation state, the local environment and the spin.
The S3 state has been studied by X-ray spectroscopy, but discrepancies occur in the literature.
Recently, high-field EPR spectroscopy revealed a bunch of different configurations of the S3 state
dependent on the sample’s treatment [1]. Consequently, the past X-ray spectroscopy studies on
S3 have been performed in inhomogeneous samples with varying mixtures of different S 3components. Herein, we studied for the first time one configuration of the S3 state inhomogeneous samples (proven by high-field EPR studies [1, 2]) by Kα Mn High Energy Resolution
Fluorescence Detection (HERFD) X-ray absorption. This method allows high-resolved spectra of
the pre-edge region that can be correlated rigorously with spectra calculated by TD-DFT. Several
models of the S3 of the current literature were tested, and the oxo-hydroxo MnIV3 model proved tobe the most consistent with the HERFD data.
[1] Chrysina et al. (2019) PNAS 116, 16841.
[2] Cox et al. (2014) Science 354, 804.

The NCSR “Demokritos” (program E11143, “He liquefier and spectroscopy”) and the Max-Planck Society(Max-Planck Partner Group program, “Study of the Photosynthetic Water splitting by Electron paramagnetic
Resonance and X-ray Spectroscopy”) are kindly acknowledged for the financial support.

The versatility of phosphonate linkers in coordination polymers
Konstantinos D. Demadis,* Elpiniki Chachlaki, Konstantinos Xanthopoulos,
Stefania Liakaki-Stavropoulou, Argyri Moschona
Crystal Engineering, Growth & Design Laboratory, Department of Chemistry,
University of Crete, Voutes Campus, Heraklion, Crete, GR-71003 Greece
Email: demadis@uoc.gr
Giulio Alberti et al. were the first to publish on metal phosphonates, by reporting on compoundsof the formula Zr(O3PR)2, where R is an alkyl or aryl group (G. Alberti, U. Costantino, S. Allulli, N.
Tomassini, J. Inorg. Nucl. Chem. 1978, 40, 1113). From these beginnings and many otherinteresting features of metal phosphonate chemistry published before 1990 it was realized, assome of the early pioneers remarked, “that a vast new field was developing”. A huge number oforganic moieties can be converted to phosphonic acids, allowing for a vast array of metal
phosphonates to be synthesized. Some phosphonic acids and their derivatives also findapplications as treatments for calcium metabolism disorders [1], corrosion inhibitors [2], flame
retardants, heavy metal chelators, organic synthesis reagents and proton conductors [3].
However, one of their principal applocations is their use as linkers for metal phosphonate MOFs
and coordination polymers.
The exponential development of metal phosphonate chemistry owes a great deal to theprogress made in the synthesis of all kinds of phosphonate linkers. In this paper we make an
attempt to comprehensively present their different classes, based on: (a) the number ofphosphonate moieties, (b) their geometrical features, (c) the relative positions of the phosphonate
groups on a specific organic fragment, (d) the presence of other functional groups on the linker,(e) the acid-base chemistry of the linker, etc.

Figure. Portion of the 1D structure of Ca-Risedronate (left). Various sulfophosphonate linkers
derived from taurine that have been used in the synthesis of metal-sulfophosphonates (right).
[1] Vassaki, M.; Papathanasiou, K.E.; Chandrinou, D; Turhanen, P.; Choquesillo-Lazarte, D.;
Demadis, K.D. Chem. Comm. 2020, 56, 5166-5169.
[2] Moschona, A.; Plesu, N.; Cabeza, A.; Thomas, A.G.; Demadis, K.D. Homologous alkyl sidechain diphosphonate inhibitors for the corrosion protection of carbon steels. Chem. Eng. J.
2021, 405, article 126864.
[3] Bazaga-García, M.; Salcedo, I.R.; Colodrero, R.M.P.; Xanthopoulos, K.; Villemin, D.; Stock,N.; López-González, M.; del Río, C.; Losilla, E.R.; Cabeza, A.; Demadis, K.D.; Olivera-Pastor,
P. Chem. Mater. 2019, 31, 9625-9634.

Employing Radicals and Bismuth in Lanthanide
Single-Molecule Magnet Design
Selvan Demir
Michigan State University, Department of Chemistry, East Lansing, MI 48824, USA
Email: sdemir@chemistry.msu.edu
Molecules that possess an energy barrier to spin inversion have intriguing potential applications
in areas such as magnetic refrigeration, molecular spintronics and high-density information
storage. For these applications, however, key performance characteristics such as large spinrelaxation barriers (Ueff) and high magnetic blocking temperatures (TB) are required. Lanthanides
have been proven to be particularly well-suited for the design of single-molecule magnets owing
to their large magnetic moments and magnetic anisotropy that stem from strong spin-orbit
coupling of the 4f orbitals. By using lanthanide ions such as Tb 3+, Dy3+, and Er3+ which possess
intrinsically large orbital angular momentum, significantly higher Ueff and TB can be achieved. A
general methodology to improve TB in multinuclear single-molecule magnets is to generate strong
magnetic exchange between lanthanide centers through the employment of radical bridging
ligands with diffuse spin orbitals that can penetrate the core electron density of the lanthanide
ions where the 4f spin orbitals lie buried. Another successful approach to strong coupling targets
the use of heavy p-block elements since their diffuse valence orbitals facilitate better penetrationof the core electron density of the lanthanide ions relative to diamagnetic ligands comprisinglighter p-block elements. Here, we will present the synthesis of multiple lanthanide singlemolecule magnets that contain radical ligands and bismuth clusters, respectively [1-3]. The latterclass of compounds were synthesized through a solution organometallic approach and represent
the first single-molecule magnets containing bismuth donors which lead to new prospects insynthetic chemistry and physics, Figure 1 [3].

Figure 1. Structure of the [Cp*2Ln2Bi6]2− dianion in a crystal of [K(THF)4]2[Cp*2Ln2Bi6].
Blue, purple, and gray spheres represent Ln, Bi, and C atoms, respectively.

[1] Delano IV, F.; Castellanos, E.; McCracken, J.; Demir, S. Chem. Sci. 2021, 12, 15219.
[2] Benner, F.; Demir, S. Chem. Sci. 2022, 13, 5818.
[3] Zhang, P.; Benner, F.; Chilton, N. F.; Demir, S. Chem 2022, 8, 717.

Multimodal Utility of Magnetic Ferrite Nanoparticles
C. Dendrinou-Samara
Department of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
Ε-mail: samkat@chem.auth.gr
Magnetic ferrite nanoparticles (MNPs) represent a reach playground for fundamental
research in magnetism while are considered among the most successful inorganic nanoparticles
in numerous applications such as biomedicine, electronic devices, catalysis, in wastewater
treatment, etc. This broad range of applications is enabled by the tunability of the composition of
the magnetic nanoscaled structures. Specifically, for bioapplications are required MNPs with welldefined composition, narrow size distribution, and high saturation magnetization values forenhanced interaction with an externally applied magnetic field. This enhancement is very
important for the successful and low dosage performance of MNPs in medicine.
We have undertaken a study1 where we focus on synthetic parameters to control the size,
composition, surface and magnetization of ferrite nanoparticles MFe 2O4 where M=Mn, Co, Ni, Zn
in an attempt to enforce their performance in bio applications. For the preparation thesolvothermal method has been selected as a simple and eco-friendly route providing productsthat exhibit high crystallinity, even for sizes under 10nm. The MNPs designed as fluorescenceagents, magnetic fluid hyperthermia heat mediators and negative contrast agents for MRI.
Moreover, shifting from the synthesis of individual MNPs to their assembly into secondary
structures, nanoclusters of the same and/or different building blocks were prepared and evaluatedfor biomedical multitasking applications. In so, magneto-fluorescent nanocomposites, magnetic
drug delivery systems, magnetic/metal–organic frameworks nanocomposites and magnetonanoadsorbents have been developed while by combining magnetic and non-magnetic featuresof NPs, heterostructures with antifungal and magnetomechanical properties have beensynthesized.
References[1] For example a) V. Georgiadou, C. Kokotidou, B. Le Droumaguet, B. Carbonnier, T. CholiPapadopoulou, C. Dendrinou-Samara, Dalton Trans., 2014, 43, 6377-6388; b) K. Giannousi, G.
Sarafidis, S. Mourdikoudis, A. Pantazaki, C. Dendrinou-Samara, Inorg. Chem., 2014, 53, 18:9657-9666; c) K. Giannousi, O. Antonoglou, C. Dendrinou-Samara. ACS Chem. Neurosci.,
2019,10, 3796-3804; d) O. Antonoglou, K. Giannousi, S. Mourdikoudis, C. Dendrinou-Samara,
Nanotechnology 2020, 31(46), 465702; e) K. Vamvakidis, N. Maniotis, C. Dendrinou-Samara,Nanoscale, 2021, 13, 6426; f) S. Lazarou, O. Antonoglou, S. Mourdikoudis, M. Serra, Z. Sofer, C.
Dendrinou-Samara, Molecules, 2023, 28, 39

Chiral Complexes from Chiral Schiff Base Ligands: The case of{Cu4Dy2} clusters
D. Dermitzaki*, A. Panagiotopoulou, M. Pissas, V. Psycharis and C. P. Raptopoulou
Institute of Nanoscience and Nanotechnology, NCSR "Demokritos", 15310, Aghia Paraskevi,
Attikis, GREECE
Email: *d.dermitzaki@inn.demokritos.gr
For more than 30 years, discrete molecular clusters that retain their magnetization in the absenceof a magnetic field below a blocking temperature, called single-molecule magnets (SMMs), havebeen proposed as potential materials for data storage and processing. Molecular materials thatcombine SMM behavior with chirality constitute a fast-growing class of multifunctional materials
for magneto-optical applications. Chirality is one of the core research topics in materials science,chemistry, physics, biology and medicine, and more recently nanoscience for emerging
technologies and applications [1,2]. Heterometallic 3d/4f coordination clusters combine electronic
properties of the respective metal ions with anisotropy induced by the lanthanides and by the useof proper chiral ligands constitute a class of magnetochiral materials for potential applications.
The use of chiral ligands ensures chirality to the derived complex which is imparted to the crystal
structures which crystallize in non-centrosymmetric polar space groups. The synthesis, structuralcharacterization and optical properties of two enantiomerically pure complexes,[Cu4Dy2(OH)2(O2CBut)7(NO3)(L-S,R)2(H2O)2] [Cu4Dy2(OH)2(O2CBut)6(NO3)2(L-S,R)2(H2O)2] with
the S- and R-enantiomers of the Schiff base ligand H2L = 2-(((1-hydroxybutan-2-yl)imino)methyl)6-methoxyphenol, are presented.

(a)(b)
Figure. (a) The molecular structure of [Cu4Dy2(OH)2(O2CBut)6(NO3)2(L-S)2(H2O)2]. (b) CD
spectra of the two enantiomerically pure complexes in dmso solutions at concentrations 5×10 -4 Μ (260500 nm) και 5×10-3 M (500-800 nm).

[1] X.Wang, S.-Q. Wang, J.-N.Chen, J.-H. Jia, C.Wang, K.Paillot, I.Breslavetz, L.-S.Long,
L.Zheng, G.L.J.A.Rikken, C.Train, X.-J.Kong, M.Atzori, J.Am.Chem.Soc. 2022, 144, 8837.
[2] H.Kuang, C.Xu, Z.Tang, Adv.Mater. 2020, 32, 2005110

Covalently-linked Supramolecular Dimers of {Mn2(μ-O)}2+ Complexes

A. Diodati,* W. Chao, S. Hill, and G. Christou

University of Florida, Chemistry Department, P.O. Box 117200, Gainesville, FL 32611, USA
Email: adiodati@chem.ufl.edu

Recent research in our group has included the synthesis and study of covalently-linked
oligomers of manganese-oxo complexes of different types as potential spin-based molecularcomponents in new 21st-century technologies. Following our many reports of dimers andtetramers of the [Mn3O(O2CR)3(mpko)3]+ single-molecule magnets (SMMs) with an S = 6 groundstate covalently-linked by dicarboxylate or dioximate linkers, which proved a wonderful resource
for the study of quantum properties such as exchange-biased quantum tunneling of magnetizationand quantum superposition/entanglement states, we have now also expanded this work tooligomers of other magnetic units. The latter has included dinuclear Mn IIIMnIV-oxo complexes withan S = ½ ground state, since we were unaware of any reports of the successful synthesis ofsupramolecular oligomers of such systems with only a single bridging dicarboxylate, our preferred
linkage approach. We have thus identified and synthesized an attractive {Mn2(μ-O)}2+ starting
complex for our purposes and explored its linkage into dicarboxylate-bridged dimers using theligand-substitution methods developed with the Mn 3 SMMs, targeting weakly exchange-coupledintra-dimer interactions. This presentation shall describe the synthesis and study of the resulting
family of [Mn2]2 dimers employing various types of dicarboxylate linkers.

Homo- and heterometallic Mn and Mn/Ln clusters bearing pyridyl
alkoxide chelates with stereogenic centers: An approach to chiralsingle-molecule magnets
D. G. Fragkis*, Th. C. Stamatatos
Department of Chemistry, University of Patras, Patras 26504, Greece
Emails: dimifrag19@gmail.com (presenting author),
thstama@upatras.gr (corresponding author)
Single-Molecule Magnets (SMMs) are zero-dimensional, molecular systems that retain theirmagnetization in the absence of an external magnetic field. Such compounds are promising for avariety of applications, such as high-density information storage and magnetic cooling [1]. Amongthe strategies for synthesizing compounds that exhibit SMM behaviour, the two most common
are: (1) the synthesis of 3d-metal clusters, in which the anisotropic metal ions areferromagnetically coupled, and (2) the synthesis of 3d/4f-metal clusters, in which high-spin 3d
metal ions and highly anisotropic 4f metal ions are combined in the same entity [1]. To this end,
N,O- chelating and/or bridging ligands, such as 2-pyridyl alcohols, and ancillary carboxylates
seem to make a suitable “ligand blend” for the preparation of high-nuclearity 3d-homometallic and3d/4f-heterometallic clusters[2]. In addition, the use of asymmetric ligands could lead to chiralpolynuclear clusters featuring a combination of interesting magnetic, electric, and structuralproperties[3].
Herein, the synthesis and characterization of a new homometallic mixed-valence {Mn12}
cluster, namely [MnII3MnIII9O8(PhCO2)11(ppm)6] (1), and two heterometallic MnIII/Dy clusters,
namely [Mn8Dy4O8(ppm)4(PhCO2)16] (2) and [Mn2Dy4O2(MeCO2)8(ppm)4(NO3)2] (3), are reported(Figure 1). In these systems, the potentially chiral ligand α-phenyl-2-pyridylmethanol (ppmH) isemployed. Furthermore, the effect of the carboxylate ancillary ligands on the nuclearity and themagnetic properties of the resulting clusters is thoroughly explored.

Figure 1: The structures of the clusters (1) (right) and (2) (left).
[1] A. Zabala-Lekuona et. al., Coord. Chem. Rev., 2021, 441, 213984.
[2] L. Pham et. al., Polyhedron, 2018, 155, 34-41.
[3] J. Mayans et. al., Dalton Trans., 2019, 48, 10427-10434.

Machine Learning Algorithms for Addressing the Gas Storage
Problem in Nanoporous Materials
George E. Froudakis*
Department of Chemistry, University of Crete, Greece
Email: frudakis@uoc.gr
Machine learning techniques (ML) are powerful tools already used in science and industry
since their computational cost is by several orders of magnitude lower than that of the“conventional” approaches. However, their ability to provide accurate predictions strongly
depends on the correct identification of those parameters (descriptors) that will allow the algorithm
to effectively learn from past data. Moreover, other critical factors that affect the quality andefficiency of the predictions are the size and the quality of the dataset used for the training of thealgorithm as well as the correct estimation of the training size.
Aiming at both, the transferability of our model and the reduction of the training data set, we
introduce 2 different classes of descriptors, based on fundamental chemical and physicalproperties: Atom Types and Atom Probes [1,2]. Our descriptors are based on the chemical
character of the atoms which consist the skeleton of the materials and not their general structuralcharacteristics, introducing in this way “chemical intuition” in our model.
On parallel, an automatic procedure of identifying the appropriate size of the training set fora given accuracy was developed [3]. A training algorithm based on “Self-Consistency” (SC)replaced the standard procedure of linearly increasing the training set. Our SC-ML methodology
leads to significantly more accurate predictions, while the number of materials needed for the
training of the ML algorithm can be reduced by an order of magnitude.
Despite the progress in the field and the improved models that have been recently developed,
ML algorithms fail to classify new materials with superior properties compared to the known ones.
To the best of our knowledge the previous point has never been addressed since extrapolation isan inherent drawback of ML. To overpass this obstacle, we propose a new methodology for theconstruction of artificial data with advanced properties that will expand the ML training set [4]. This
will enable ML algorithms to achieve accurate predictions even for materials with properties way
out of those found in the original training set.
References:[1] G.S Fanourgakis, K. Gkagkas,, E. Tylianakis, E. Klontzas, G.Froudakis, , The Journal of
Physical Chemistry A, 2019 123, 6080
[2] G.S Fanourgakis, K. Gkagkas,, E. Tylianakis, G.Froudakis, , Journal of the American Chemical
Society, 142 2020 142, 3814
[3] G.S Fanourgakis, K. Gkagkas,, E. Tylianakis, G.Froudakis, The Journal of Physical ChemistryC, 2020, 124, 19639[4] G.S Fanourgakis, K. Gkagkas,, G.Froudakis, The Journal of Chemical Physics, 2022, 156,
054103

Molecular Spin Qubits Based on High-Symmetry Lanthanide
Complexes
Miguel Gakiya-Teruya 1, Robert Stewart 2, Stephen Hill 2, Michael Shatruk 1

1. Chemistry and Biochemistry, Florida State University, Tallahassee, FL, United States.
2. Physics, Florida State University, Tallahassee, FL, United States.
Email: mg19y@fsu.edu

Qubit is an elementary unit of quantum computing, allowing coherent superposition of statesthat can be initialized, manipulated, and read-out for quantum information processing. One ofthe platform that have taken the attention due to their synthetic tunability and a broad range ofspin states that can be incorporated by using various transition and lanthanide metal ions are
the Molecular spin qubits. The generally short coherence time, however, remains the major
obstacle for implementation of molecular qubits in quantum computing technology. Have been
tried different approach to increase the coherent time of the molecular qubits. In thiscontribution, we demonstrate how this challenge can be addressed by using high-symmetry
lanthanide complexes to achieve clock transitions, characterized by a dramatically enhanced
coherence time at specific values of resonant magnetic field. The emergence and frequency ofthe clock transition are intimately related to the local symmetry of the lanthanide coordination
environment. This relationship will be discussed, and steps to design assemblies of clocktransition qubits will be suggested.

Volatile Organic Compounds Sensed by Iron(II) Sensors
Yann Garcia*
Institute of Condensed Matter and Nanosciences (IMCN/MOST), Place Louis Pasteur 1, 1348
Louvain-la-Neuve, Belgium
Email: yann.garcia@uclouvain.be
In recent years, attention has been focused on the efficient detection of chemical pollutants,
especially small volatile organic compounds (VOCs) and hazardous gases (HGs). VOCs caneasily enter the body through breathing, and cause serious health issues. Our investigations led
us to focus on a series of mononuclear azole based complexes, as well as on spin crossovercapsules. For instance, [Fe(H2btm)2(H2O)2]Cl (1) (H2btm = di(1H-tetrazol-5-yl)methane), which
can detect at real time, with a high selectivity and ultra-sensitivity, 14 VOCs and HGs [1]. In
particular amines, which are detected quickly (< 2 min). The detection is accompanied bysignificant and fast colour changes detectable by the naked-eye at ambient conditions or by asmartphone-based colorimetric method. After VOCs adsorption, a spin state occurs, which wasprobed by 57Fe Mössbauer spectroscopy. In addition to its high thermal stability (up to 170 °C), 1
showed excellent reusability by consecutive seven cycles of adsorption–desorption. This sensor
is low-cost, environmentally friendly, easy to use, and shows fast detection performances. Suchfeatures offer attractive prospects for 1 which could be used for in-field detection and food safetycontrol in environmental conditions, e.g. for meat freshness control [2]. In this lecture, I will review
latest advances highlighting the impact of our iron(II) complexes, used as sensors for various toxic
industrial chemicals (TICs) [3].

Figure. Using a supramolecular capsule to probe meat freshness [3].

[1] L. Sun, A. Rotaru, K. Robeyns, Y. Garcia, Ind. Eng. Chem. Res., 2021, 60, 8799.
[2] W. Li, L. Sun, C. Liu, A. Rotaru, K. Robeyns, M. L. Singleton, Y. Garcia, J. Mater. Chem. C,
2022, 10, 9216. Hot paper. Front cover.
[3] L. Sun, A. Rotaru, Y. Garcia, J. Hazardous Mater., 2022, 437, 129364. IMCN news

Self-Therapeutic Nanostructures: The case of Zn-based Nanoparticles
K. Giannousi* & C. Dendrinou-Samara
Laboratory of Inorganic Chemistry, Department of Chemistry, Aristotle University ofThessaloniki, Thessaloniki, 54124, Greece
Email: klegia@chem.auth.gr
Metal nanoparticles and metal oxides have emerged as promising tools in the field of biomedicine,since they can be used as biomedical agents and/or innovative drug delivery systems for thetreatment and diagnosis of a variety of disorders. In an attempt to pass from the bench to clinics,
we are focus on the development of zinc-based nanostructures with self-therapeutic potential.
Zinc oxide nanoparticles (ZnO NPs) are one of the most important members of metal oxides,
constituting possibly the safest and most environmentally friendly metallic nanomaterial. ZnO NPs
have been solvothermally prepared and evaluated as multimodal agents in neurodegenerative
diseases. Hexagonal shaped naked ZnO NPs with inherent anti-amyloidogenic and antioxidant
activity have been further immobilized with alizarin (Alzn) molecules to act as biomarkers withpredictive and imaging ability. Facing the serious health concern of the ongoing crisis of
antimicrobial resistance, polyol coated Zn-based NPs, such as ZnO, and bimetallic copper-zinc(CuZn) NPs, have been synthesized in order to be studied as potential efflux pump inhibitors.
Apart from their intrinsic antimicrobial properties proved against pathogenic bacteria, their coadministration with commercial antibiotics was applied as a modern strategy to kill resistantbacterial species. Moreover, among copper-based nanoparticles, CuO NPs have also been
included in this study due to their antibacterial efficacy against a range of Gram-positive andGram-negative strains. In the terrain of central nervous system diseases, ZnO NPs either
PEGylated or coated with amines, have been further loaded with drugs, such as adamantane
carboxylic acid and memantine, to support their competence to interact with DNA in combination
with protein amyloidosis phenomena.

[1] K. Giannousi, M.-E. Karageorgou, I. M. Oikonomou, P. Komninou C. Dendrinou-Samara, J.
Inorg. Biochem., 2022. doi: 10.1016/j.jinorgbio.2022.111971, PMID: 36049260.
[2] I. Eleftheriadou, K. Giannousi,* E. Protonotariou, L. Skoura, M. Arsenakis, C. DendrinouSamara, & A. Sivropoulou, ACS Applied Nano Materials 2021, 4, 9, 9799–9810.

Novel synthetic approaches for the development of functional 2D
hybrid materials for energy, environmental and biomedical
applications
Dimitrios P. Gournis
Department of Materials Science and Engineering, University of Ioannina, 45110
Ioannina, Greece
Abstract
Much of the research effort on 2D materials focuses on its use as building block for thedevelopment of novel hybrid structures with well-defined dimensions and behavior suitable forapplications among else in gas storage, heterogeneous catalysis, gas/liquid separations,nanosensing and biology. Towards this aim, novel nanostructured pillared materials based ongraphene-based matrices (graphene, graphene oxide and graphite nitrate)1-9 and other 2D
materials10-15 like germanane (GeH) with high surface area, tunable pore size and aromaticfunctionalities have been synthesized and studied by using top-down (bulk synthesis) and bottomup (by combining the Langmuir-Schaefer and the self-assembly techniques) synthetic
approaches. Hybrid materials were characterized by a combination of analytical techniques.
Representative case studies addressing cutting edge processes of great importance such as theuse of these hybrid nanostructures as catalysts, phase change materials, cytotoxic agents,
effective adsorbents for environmental remediation, conductive inks and gas (H 2 and CO2)
storage materials will be discussed.
References
1. E. Thomou, V. Sakavitsi, G. K. Angeli, et al. RSC Advances, 2021, 11, 13743
2. K. Spyrou, L. Kang, E.K. Diamanti, et al. Carbon, 2013, 61, 313.
3. T. Tsoufis, G. Tuci, S. Caporali, et al. Carbon, 2013, 59, 100.
4. K. Spyrou, G. Potsi, E.K. Diamanti, et al. Adv. Funct. Mater., 2014, 24, 5841.
5. K. Spyrou, M. Calvaresi, E.A.K. Diamanti, et al. Adv. Funct. Mater., 2015, 25, 263.
6. T. Tsoufis, Z. Syrgiannis, N. Akhtar, et al. Nanoscale, 2015, 7, 8995.
7. V. Georgakilas, A. Demeslis, E. Ntararas et al. Adv. Funct. Mater., 2015, 25, 1481.
8. A. Kouloumpis, K. Spyrou, K. Dimos et al. Front. Mater., 2015, 2, art. 10.
9. N. Chalmpes, M. Patila, A. Kouloumpis et al. ACS Appl. Mater. Interfac. 2022, 14, 26204.
10. T. Giousis, G. Potsi, A. Kouloumpis, et al.. Angew. Chem.- Inter. Ed., 2021, 60, 360.
11. Q. Chen, L. Liang, G. Potsi, et al. Nano Letters, 2019, 19, 1520.
12. A. Kouloumpis, A. V. Chatzikonstantinou, N. Chalmpes, et al. ACS Appl. Nano Mater., 2021, 4, 2333
13. B. N. Madhushankar, A. Kaverzin, T. Giousis, et al. 2D Materials 2017, 4, 021009
14. T. Giousis, S. Fang, M. Miola, et. al. J. Environm. Chem. Engineer. 2023, 11, 109784.
15. A. Koutsioukis, G. Florakis, S. Samartzis, et. al. J. Mater. Chem. C 2023, 11, 3244
Acknowledgments. Part of this research has been co-financed by the European Regional Development Fundof the European Union and Greek national funds through the Operational Program Competitiveness,
Entrepreneurship and Innovation, under the call RESEARCH—CREATE—INNOVATE (project codes: Τ2ΕDΚ00955 and T2EDK-02171).

Catalysis of a Diels-Alder Reaction Between Azachalcones andCyclopentadiene by a Recyclable Copper(II) Metal-Organic Framework
Eleni Hadjikyprianou*, Sotiris Petrides, Andreas Kourtellaris, Anastasios J. Tasiopoulos andSavvas N. Georgiades
Department of Chemistry, University of Cyprus, 1678, Nicosia, Cyprus
Email: hadjikyprianou.eleni@ucy.ac.cy
Metal-organic frameworks (MOFs) have attracted considerable interest as emerging
heterogeneous catalysts for organic transformations of synthetic utility. Herein, a Lewis-acidic
MOF,{[Cu3(PEIP)2(5-NH2-mBDC)(DMF)]·7DMF}∞(PEIPH2=5-((pyridin-4ylmethylene)amino)isophthalic acid, 5-NH2-mBDCH2 = 5-amino-1,3-benzenedicarboxylic acid),denoted as Cu(ΙΙ)-PEIP, has been synthesized and deployed as an efficient heterogeneous
catalyst for a Diels-Alder cycloaddition. Specifically, the [4+2] cycloaddition of 14 substituted
azachalcone dienophiles with cyclopentadiene has been investigated. MOF-catalyzed reaction
conditions were optimized, leading to the selection of water as the solvent, in the presence of
sodium dodecyl sulfate (SDS) to address substrate solubility. The Cu(II)-PEIP catalyst showed
excellent activity under these conditions, exhibiting comparable or, in some cases, superior
efficiency to a homogeneous catalyst often employed in Diels-Alder reactions, namely Cu(OTf) 2.
The nature of the azachalcone fragment substituent played a significant role in the reactivity ofthe dienophiles, with electron-withdrawing (EW) substituents enhancing conversion and electrondonating (ED) ones exhibiting the opposite effect. Coordinating substituents appeared to enhancethe endo selectivity. Importantly, the Cu(II)-PEIP catalyst can be readily isolated from the reaction
mixture and recycled, up to four times, without any significant reduction in conversion or
selectivity.

Figure. Schematic illustration of the catalytic properties of Cu-PEIP catalyst.

Molecular Analogues of the Structure and Spin Vector Ordering of
LnMnO3 Manganite Perovskites
Ashlyn R. Hale,* Cédric Pécou, Khalil A. Abboud, George Christou
Department of Chemistry, University of Florida, Gainesville, FL 32611, USA:
Email: ashlyn.rose.hale@ufl.edu
Molecular perspectives of vital homo- and heterometallic metal oxides have proven to be quite
valuable. Utilizing bottom-up synthetic methodologies, our group has successfully generated a
versatile library of ‘molecular metal oxide nanoparticles’ (MNPs), which are monodisperse metaloxo clusters that mimic the structure of the parent oxide as confirmed by single-crystal X-ray
crystallography. Furthermore, the true solubility of these materials enables their completecharacterization via various solid-state and solution-phase techniques, allowing for atomicallyprecise interpretation of structure-property relationships unknown or ambiguous in the bulk andnanomaterials. Our first forays focused on cerium dioxide (CeO 2) with the fluorite structure andAMnO3 manganites with the perovskite structure (Figure A, C). The former is of widespread
importance for industrial, environmental, and biomedical catalysis, while the latter offer
ferromagnetic, ferroelectric, and multiferroic properties relevant to new technologies.
Since our initial discoveries of the largest CeO 2 MNP at the time (Ce40) [1] and the firstmolecular analogue of the CeMnO3 perovskite repeating unit (Ce3Mn8) [2], our MNP program hasflourished (Figure B, D). To date, we have generated a family of CeO 2 MNPs with varying
nuclearities up to 100, while the CeMnO3 project has seen the development of a family of Ce3Mn8
complexes featuring various ligands. The latter was inspired by the rich literature regarding thedifferent spin vector ordering modes in bulk magnetic perovskites and DFT predictions of modechanges by external stimuli such as pressure. Our initial Ce3Mn8 cluster exhibited the sameground state spin vector ordering as C-type AF (antiferromagnetic) bulk perovskites (Figure E)
with low-lying A-type AF (Figure F) excited states. This suggested that small structural
perturbations via changes in the ligation environment might allow us to change the ground state
to A-type AF. In this work, synthetic efforts have been extended to further corroborate thishypothesis. In addition, a new Ce/Mn/O complex has been synthesized, showing structuralfeatures relevant to both CeO2 and CeMnO3, providing further support for our rationalization of
the perovskite-like spin vector ordering observed in our molecular mimics.

A

B

C

D

E

F

Figure. (A) CeO2 fluorite lattice (B) Ce40 MNP (C) ABO3 perovskite (D) Ce3Mn8 core (E) C-type AF spin
vector ordering (F) A-type AF spin vector ordering[1] Mitchell, K. J.; Abboud, K. A.; Christou, G. Nature Commun. 2017, 8, 1445.
[2] Thuijs, A. E.; Li, X.-G.; Wang, Y.-P.; Abboud, K. A.; Zhang, X.-G.; Cheng, H.-P.; Christou, G. Nature
Commun. 2017, 8, 500.

Application of wideband pulsed high-frequency EPR to molecularquantum spin science
S. Hill,* M. V. H. Subramanya, E. Salerno, K. Kundu, J. Marbey
National High Magnetic Field Laboratory, Florida State university, Tallahassee, FL32309, USA
Email: shill@magnet.fsu.edu
This presentation will provide an overview of a range of new applications in the area ofmolecular quantum spin science that are now possible at the US National High Magnetic Field
Laboratory as a result of the development of a wideband, high-power 94 GHz pulsed EPR
spectrometer [1]. This instrument allows true Fourier-transform detected experiments spanning a
1 GHz instantaneous bandwidth, akin to what has been possible in NMR for several decades.
The presentation will begin by describing experiments on a nitroxide radical using chirped pulses,
enabling acquisition of the full spectrum in a single sequence, thus providing a very efficient andconvenient means to measure the field orientation dependence of the spin-lattice relaxation time,
T1. This will be followed by a discussion of a coherent population transfer protocol involving the2S + 1 = 8 Zeeman levels associated with the spin S = 7/2 Gd3+ ion, potentially paving the way
towards implementation of well-known quantum search algorithms. It will also be shown how theuse of chirped pulses provides a route to achieving highly non-thermal spin populations,suggesting novel initialization schemes.

Figure. (a) Normalized 3D plot of 50 K FT spectra of 0.25 mM TEMPOL as a function of delaytime, 𝜏𝑟 , using an inversion recovery pulse sequence at B = 3.3445 T; blue denotes inverted
population and red is equilibrium. (b) 2D false color map corresponding to the data in (a); a
representative long delay time spectrum is shown at top.
This work was supported by the US Department of Energy (under DE-SC0020260 to S.H.)
and the Center for Molecular Magnetic Quantum Materials (M2QM), an Energy Frontier ResearchCenter funded by the US Department of Energy, Office of Science, Basic Energy Sciences underAward DE-SC0019330. Experimental work performed at the National High Magnetic Field
Laboratory is supported in part by the National Science Foundation (under DMR-1644779) andthe State of Florida.
[1] M.V.H. Subramanya, J. Marbey, K. Kundu, J. E. McKay, S. Hill, Appl. Magn. Reson., 2023,
54, 165. https://doi.org/10.1007/s00723-022-01499-3

Structure-Property Studies of Paramagnetic Group V Carbenes
S. M. Holmes,* F. Shen, M. Eissler
Department of Chemistry and Biochemistry, University of Missouri-St. Louis, St. Louis, Missouri
63121, USA
Center for Nanoscience, University of Missouri-St. Louis, St. Louis, Missouri 63121, USA
Email: holmesst@umsl.edu
Transition metal N-heterocyclic carbene complexes find extensive use in catalysis, medicinal,materials, and surface science applications. While numerous paramagnetic 3d complexes are
known comparatively fewer 4d and 5d analogues have been described. Carbene ligands are
generally considered to be competent  donors in transition metal complexes owing to the radialextent and higher energies of the carbon-centered highest occupied molecular orbital. Latetransition metal single-molecule magnets offer a variety of promising features relative to their 3dcounterparts. First, heavier transition metal ions should generally have stronger metal-ligand
bonds than 3d derivatives, owing to efficient orbital overlap with the carbene HOMO. Second,enhanced metal-ligand covalency, particularly with rigid ligands are present, should discourage
vibronic interactions that reduce symmetry of the complexes. Third, in comparison to 3d ions,considerably higher spin-orbit parameters are anticipated for the 4d and 5d series, roughly scaling
with atomic number which may engender higher magnetic anisotropy.
Another approach exploits control of spin-lattice relaxation by minimizing thermally populated
excited state spin levels particularly in the absence of ligand-centered nuclear spins. Among theseare several VIV (S = ½) complexes where long relaxation times are often observed offering theprospect of a tunable spin-qubit platform for molecule-based information storage applications. A
survey of the chemical literature indicates that niobium(III,IV) complexes are underexplored incomparison to their 3d congeners, with most reports being limited to cyanide, pyridyl, phosphine,and phosphine oxide derivatives. Among these are Nb IVX4(py)2 (X = Cl, Br, I) complexes whose
magnetism deviates from spin-only behavior [e.g., eff(B) = 1.37, Cl; 1.26, Br; 1.05, I] where small
g parameters (g ≤ 1.58) are also found, suggesting halide bonding and orbital contributions may
be important. In this presentation, we will describe recent efforts to develop a modular approach
using N-heterocyclic carbene (Figure 1) ancillary ligands for the deliberate preparation ofcomplexes, whose magnetic properties are tuned via ligand steric demand and donor strengths.

Figure 1. (left) X-ray structure for 1. (middle) T vs T data for NbCl4(IMes)2 (1), NbCl3(IMes)2 (2), andNbOCl2(IMes)2 (3). Lines represent PHI fitting of data. (right) ´´ vs T data for 1 (Hdc = 6 kOe; Hac = 3
Oe).

New Insights in The Magnetic Anisotropy of Single-Molecule Magnets

Zahra Hooshmand and Mark R Pederson
Department of Physics, University of Texas at El Paso
El Paso, Texas, United States 79968

Email: zhooshmand@utep.edu

For the past thirty years, single-molecule magnets (SMMs) have been considered as a new routeto store information. When the bi-stable ground state of these molecules is combined with theirsmall size, it can provide memory units which are thousands of times denser than the conventional
devices. The bottleneck is to achieve temperatures high enough to have these units as functional
devices, in room temperature. So far, there have only been a few studies done on transition-metal
based SMMs where a relatively high magnetic anisotropy has been achieved. In this talk, I will
present results of a study on different single molecule magnets with Mn [1], Co [2], and Fe centerswhere different mechanisms to control their magnetic anisotropy have been predicted from firstprinciples calculations. I will show how theory can predict new molecular structures for practicalapplications.

[1] Z Hooshmand, MR Pederson, PCCP, 2020, 22 (47), 27547.
[2] Z Hooshmand, JX Yu, HP Cheng, MR Pederson, PRB, 2021, 104 (13), 134411.

The S3 state of the oxygen evolving complex of spinach Photosystem II.
N. Ioannidis
National Centre of Scientific Research “Demokritos”, Institute of Nanoscience andNanotechnology, Patr. Gregoriou E & 27 Neapoleos Str, Agia Paraskevi, 15341, Greece.
Email: n.ioannidis@inn.demokritos.gr
In cyanobacteria, algae, and plants water oxidation achieved by Photosystem II (PSII)
constitutes a fundamental biochemical process empowering life on Earth, and setting theparadigm for engineering solar fuel–production systems. The Oxygen Evolving Complex (OEC)of PSII contains an inorganic Mn4CaO5 cluster whose catalytic cycle involves four light-driven
oxidation states, called S-states. During one cycle 4 electrons and 4 protons are removed fromtwo bound water molecules and one molecule of O 2 evolves. We used Electron Paramagnetic
Resonance (EPR) spectroscopy to show that the S3 state of OEC (one oxidation step prior to O 2
release) contains two magnetically distinct populations, which are characterized by spins states
S=3 and S=6 [1]. The heterogeneous nature of S3 is reflected on its reaction to near infrared light(NIR) excitation. Absorption of NIR light results in two events: (i) the appearance of a modified S 2state concurrent with the oxidation of a nearby tyrosine amino acid residue to tyrosyl radical (Y Z
rad), and (ii) the appearance of a metastable S3 state characterized by a different EPR spectrum[2]. This structural heterogeneity of the S3 state, provides constraints on the S3 to S4 transition, on
substrate identity and delivery pathways, and on the mechanism of O-O bond formation.
S3
S=3 and 6

NIR

"S2"

NIR
YZ rad

e-

'

"S3 "

0

1000

2000

3000

4000

5000

Gauss

Figure. NIR excitation of the S3 state.
[1] G. Zahariou, N. Ioannidis, Y. Sanakis and D. A. Pantazis. Angew. Chem. Int. Ed. 2021, 60,
3156 – 3162.
[2] N. Ioannidis, J. H. A. Nugent and V. Petrouleas. Biochemistry, 2002, 41, 9589 – 9600.

Nanostructure-driven magnetic phenomena
in transition-metals high-entropy alloys
A. Jelen*, P. Koželj, S. Vrtnik, J. Luzar, M. Wencka, J. DolinšekJožef Stefan Institute, (Ljubljana), Slovenia
Email: andreja.jelen@ijs.si
High-entropy alloys (HEAs) represent novel metals-based materials with complicatedmicrostructures, where at least five different chemical elements, all in majority concentrations, aremixed on a simple crystal lattice. Likewise, the materials are usually comprised of more than one
phase on different microscopic levels, ranging from a few nm to 1 mm. The complex atomic andphase structure, together with the choice of the elements and their concentrations, determine thephysical properties (magnetic, electric and thermal) of the HEAs, which are usually not just thecompositional average of physical properties of the constituent phases.
In the present invited lecture, three different transition-metals-based HEAs will be presented bytheir structure and magnetic properties. They all possess specific two-phase nanostructure, which
influences the magnetic behavior of the bulk HEA material accordingly. FeCoCrMnAl [1] is a single
crystal with a two-phase structure that leads to two successive magnetic phase transitions above
the room temperature. This makes the material a promising candidate for the application inmagnetocaloric refrigeration. FeCoNiPdCu [2] is the first magnetically soft high-entropy alloy
which performs comparably to the best commercial soft magnets for static and low-frequency
applications. AlCoFeNiCu [3] is a material that possess a combination of excellent magnetic
softness and vanishing magnetostriction. This is beneficial for the applications that needsupersilent (inaudible to a human ear) materials, like transformers, magnetocaloric coolers, andother “humming” electromagnetic machinery.

Figure. Nanostructures of two-phase magnetically diverse high-entropy alloys.
They are all Z-contrast images of two-phase high-entropy alloys: a) HAADF STEM image of the
FeCoNiPdCu HEA material [2], b) BS SEM image of the AlCoFeNiCu HEA material [3] andc) BS FIB image of the FeCoCrMnAl HEA material [1].
[1] A. Jelen, et al., J. Alloys Compd., 2021, 864, 158115.
[2] P. Koželj, S. Vrtnik, A. Jelen et al. Adv. Eng. Mater., 2019, 21, 1801055[3] J. Luzar, P. Priputen, M. Drienovský, S. Vrtnik, P. Koželj, A. Jelen, et al., Adv. Mater. Interfaces,
2022, 9, 2201535.

No End of History for Chemistry Education and Magnetic Resonance
Christopher W. M. Kay
Physical Chemistry and Chemistry Education, Saarland University, Saarbrücken, Germany;
London Centre for Nanotechnology, University College London, London, UK
Email: Christopher.kay@uni-saarland.de; c.kay@ucl.ac.uk
In this talk, I will discuss two themes that are currently the focus of my group’s work:
Chemistry Education. Bloom's Taxonomy of Learning [0] divides educational learning objectives
into three domains: cognitive; affective; and psychomotor. Within each domain, there are several
stages. The cognitive domain remains a primary focus of education, and as illustrated in the figure,university students generally start at the lowest level, by learning facts. As they progress from
BSc to MSc to PhD, it is essential that students ascend the hierarchy and develop the ability tosynthesize new knowledge. Unfortunately, we are constantly confronted by the heterogeneity offreshmen students in terms of their (inadequate) prior knowledge and the challenge of assistingthem in successfully making the transition from school to university. Furthermore, the traditionalrole of lectures as places where information is passively imparted is – with the advent of theinternet – essentially outdated, rather it is necessary to support students in the development of
their cognitive abilities. It is beginning to be recognized that his requires a completely different
approach to education. Here I will outline some ideas with which we have been experimenting,including the embedding of coding in physical chemistry courses to help students develop a morestructured approach to learning.

Figure. Adapted from the Cognitive Domain of Bloom’s Taxomony of Learning 1956, updated 2001

EPR Spectroscopy. I will describe our recent contributions to the development of catalysts as
highly efficient peroxymonosulfate activators for the efficient degradation of persistent organic
pollutants using spin-trapping and EPR spectroscopy [1,2].
[0] Taxonomy of Educational Objectives, Handbook I: The Cognitive Domain." New York: David
McKay Co Inc, Bloom. 1956.
[1] Synthesis of novel LaCoO3/graphene catalysts as highly efficient peroxymonosulfate activator
for the degradation of organic pollutants, Hammad et al., Chemical Engineering Journal, 2023,
454, 139900[2] Enhanced heterogeneous activation of peroxymonosulfate by Ruddlesden-Popper-type
La2CoO4+delta nanoparticles for bisphenol A degradation, Hammad et al., Chemical Engineering
Journal, 2022, 429, 131447

Mechanism of the Reductive Activation of O2 to O22- from a
Vanadium(IV) Species and Its Potential Use in Fuel Cells
Anastasios D. Keramidas,* Michael Papanikolaou, Sofia Hadjithoma Odysseas Keramidas,
Chryssoula Drouza, Aggelos Amoiridis, Alexandros Themistokleous, Sofia C. Hayes, Panagiotis
Lianos, Athanassios C. Tsipis, Themistoklis A. Kabanos

Department of Chemistry, University of Cyprus, Nicosia 2109, Cyprus.
E-mail:akeramid@ucy.ac.cy

The two electron reductive activation of O 2 to O22- is of particular interest to scientificcommunity mainly due to the use of peroxides as green oxidants and in powerful fuel-cells. Amongthe metal-ions which activate O2, vanadium is of particular interest because of its numerous
oxidative catalytic properties. Reaction of either VIVOSO4.3.5H2O or VIVOCl2 with N-(8quinolyl)pyridine-2-carboxamide (Hpbq) in CH3OH solution under atmospheric O2, at room
temperature, resulted in the quick formation of [VVO(k2-O2)(pbq)(H2O)](1). Compound 1
constitutes a rare example of formation of a (peroxo)oxidovanadium(V) complex from molecular
O2 and an oxidovanadium(IV) complex. The reaction of formation of compound 1vs. time wasmonitored by 51V and 1H NMR, UV-vis, cw-X-EPR, Resonance Raman spectroscopiesand cyclic
voltammetry revealing the formation of a stable radical intermediate [V VO(k2-O2)(pbq)(H2O)]•+.
Dynamic experiments in combination with computational calculations were used to elucidate themechanismofthereaction.
Thegalvanic
cell{Zn|V III,VII||cis-[VVO2(bpq)],[VVO(O2)(bpq)(H2O)],[VIVO(bpq)(H2O)2]+|O2|C(s)} was manufactured, demonstrating that thistechnology can be used in Zn|H2O2 fuel cells generating H2O2 in situ from atmospheric O2.

Zero-Field Splitting and Slow Magnetization Relaxation in Mononuclear 3d-Metal
Complexes
Panayotis Kyritsis
Inorganic Chemistry Laboratory, Department of Chemistry, National and Kapodistrian Universityof Athens, 15771 Athens, Greece
e-mail: kyritsis@chem.uoa.gr
Ever after 2010,[1] a large number of mononuclear 3d-metal complexes have been shown to
exhibit slow relaxation of magnetization, often associated with the presence of significant zerofield splitting (zfs).[2-3] Magnetometry and various spectroscopic techniques, such as highfrequency and -field EPR (HFEPR) and Far-IR Magnetic Spectroscopy (FIRMS), are methods ofchoice for the determination of the latter.[4] The coordination chemistry of the {R2P(E)NP(E)R2}−
ligands (E = O, S, Se; R = alkyl or aryl group) towards transition metal elements has been shown
to be rather versatile.[5] Specific examples of S = 1 tetrahedral Ni(II),[6] S = 2 octahedral Mn(III)[7] and tetrahedral Fe(II),[8] as well as S = 3/2 tetrahedral [9,10] and octahedral [11] Co(II)complexes. bearing these ligands and exhibiting either large zfs or slow relaxation ofmagnetization. will be discussed. In addition, spectroscopic and electrocatalytic studies on novel
S = 3/2 tetrahedral Co(II) complexes of the general type CoS2Cl2, S = thiosemicarbazone ligand,will be presented. A similar CoS2Cl2-type complex has recently been shown to be anelectrocatalyst for the hydrogen evolution reaction (HER).[12]1.

D. E. Freedman, W. H. Harman, T. D. Harris, G. J. Long, C. J. Chang, J. R. Long, J. Am. Chem. Soc. 132, 1224
(2010)
2. M. Feng, M. L. Tong, Chem. Eur. J. 24, 7574 (2018)
3. P. S. Perlepe, D. Maniaki, E. Pilichos, E. Katsoulakou, S. P. Perlepes, Inorganics 8, 39 (2020)
4. J. Krzystek, J. Telser, Dalton Trans. 45, 16751 (2016)
5. C. Silvestru, J. E. Drake, Coord. Chem. Rev. 223, 117 (2001)
6. S.-D. Jiang, D. Maganas, N. Levesanos, E. Ferentinos, S. Haas, K. Thirunavukkuarasu, J. Krzystek, M. Dressel,
L. Bogani, F. Neese, P. Kyritsis, J. Am. Chem. Soc. 137, 12923 (2015)
7. Y. Sanakis, J. Krzystek, D. Maganas, A. Grigoropoulos, E. Ferentinos, M.G. Kostakis, V. Petroulea, M. Pissas, K.
Thirunavukkuarasu, W. Wernsdorfer, F. Neese, P. Kyritsis, Inorg. Chem. 59, 13281 (2020)
8. S. A. Stoian, M. Moshari, E. Ferentinos, A. Grigoropoulos, J. Krzystek, J. Telser, P. Kyritsis, Inorg. Chem. 60, 10990(2021)
9. S. Sottini, G. Poneti, S. Ciattini, N. Levesanos, E. Ferentinos, J. Krzystek, L. Sorace, P. Kyritsis, Inorg. Chem. 55,
9537 (2016)
10. E. Ferentinos, D. Tzeli, S. Sottini, E.J.J. Groenen, M. Ozerov, G. Poneti, K. Kaniewska-Laskowska, J. Krzystek,
P. Kyritsis, Dalton Trans. 52, 2035 (2023).
11. E. Ferentinos, M. Xu, A. Grigoropoulos, I. Bratsos, C. P. Raptopoulou, V. Psycharis, S.-D Jiang, P. Kyritsis, Inorg.
Chem. Front. 6, 1405 (2019)
12. L. S. Bezerra, P. P. Rosa, G. V. Fortunato, L. Pizzuti, G. A. Casagrande, G. Maia, J. Mater. Chem. A, 6, 19590(2018)

Acknowledgments I would like to thank all my collaborators for their invaluable contribution
to this work, as well as the Special Account for Research Grants of the National andKapodistrian University of Athens for financial support.

Spin State Switching in Non-centrosymmetric Crystals
Z. G. Lada,* A. Sultan, S. Sundaresan, D. McLaughlin, H. Müller-Bunz, G. G. Morgan
School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland
Email: zoi.lada@ucd.ie
Materials with multiple functionalities offer great potential for technological development.
Complexes which show spin state switching are good candidates to make multifunctional
materials due to the ease of chemical modulation which enables facile integration of otherproperties. We have recently observed a preference for crystallization in non-centrosymmetricspace groups within a series of iron(III) complexes with hexadentate Schiff base chelating
ligands.1 We have also noted the tendency for ligand disorder in the same complex family andthis yields both the meso and non-meso orientations for the NH groups on the ligand framework,
Figure. We explore here the scope of this effect and whether the two phenomena are related.
We report structural, spectroscopic and magnetic data on several iron(III) complexes with different
chelating ligands and counterions. For example, we compare the Cl- and BPh4- salts of [Fe(5Fsal2333)]+, which show different spin states between 5-300 K, with one being high spin and theother low spin, with onset of a gradual and incomplete spin crossover on warming to room
temperature. Structural investigation reveals different orientations of the hydrogen atoms on thesecondary amine donors in the two salts of the [Fe(5F-sal2333)]+ cation: high spin complex[Fe(5Fsal2333)]Cl crystallizes with non-meso orientations while the spin crossover complex [Fe(5Fsal2333)]BPh4 crystallizes with a combination of meso and non-meso orientations disordered over
one crystallographic site. We show here recent results on the use of Raman spectroscopy to study
the complex conformations and how these may change on attachment of the complexes to avariety of surfaces.

Figure. Hydrogen atoms at the amine nitrogen of the R-Sal2333 backbone, forming the non-meso
Type A form (left) and meso form (middle) of the ligand. Co-crystallization of both modes (right)
was observed in [Fe(5F-sal2333)]BPh4 and this crystallization mode was termed Type B.
[1] S. Sundaresan, I. A. Kühne, C. T. Kelly, A. Barker, D. Salley, H. Müller-Bunz, A. K. Powell, G.
G. Morgan, Crystals, 2019, 9, 19.

Observation of Two-Step Spin Transition in Iron(II) 4-amino-1,2,4triazole Based Spin Crossover Nanoparticles
Nikolia Lalioti,*1 Efstathia Giannopoulou,1 Alexander Charitos,1 John Parthenios,2 Ondrej Malina,3Michaela Polaskova3 Alexandros Kalarakis4 Vassilis Tangoulis1
1

Department of Chemistry, Laboratory of Inorganic Chemistry, University of Patras, 26504,
Patras, Greece.
2
Institute of Chemical Engineering Sciences, Foundation of Research and Technology-Hellas(FORTH/ICE-HT), Stadiou Street, Platani, Patras, 26504 Greece
3
Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology
and Research Institute (CATRIN), Palacký University Olomouc, Křížkovského 511/8, 77900,
Czech Republic.
4
Department of Mechanical Engineering, University of the Peloponnese, 26334 Patras,
GreeceEmail: lali@upatras.gr
The temperature dependent spin state change of iron(II) from low-spin (S=0) to high-spin(S=2), known as spin crossover phenomenon (SCO), which is further accompanied by large
thermal hysteretic phenomena at temperatures ideally close to RT or above, has widened thehorizons in the field of nano structuration of molecule-based devices. It is therefore of utmost
importance to correlate the SCO properties as a function of the size of SCO nanoparticles.
In this talk we will present a synthetically controllable two-step transition that was observedin Fe(II) SCO NPs of the dehydrated 1- dimensional coordination polymer [Fe(NH 2trz)3]Br2 (NH2trz= 4-amino-1,2,4-triazole) using the reverse micellar method. Different profiles of two-step
hysteresis was observed in certain synthetical protocols and a drastic change in the magnetic
characteristics towards a one-step hysteresis was noted by changing the time of the reaction. In
all cases the critical temperatures observed are well above the values expected for[Fe(NH2trz)3]Br2∙xH2O, while a sweeps rate dependence of the hysteretic profile revealed for the
first time . A Raman laser-assisted protocol also used to initiate and monitor the SCO effect of theNPs.[1][1] N. Lalioti, E. Giannopoulou, A. Charitos, J. Parthenios, O. Malina, M. Polaskova, A. Kalarakis,
V. Tangoulis, Dalton Trans., 2023, 52, 2937.

"Τhis paper has been financed by the funding programme “MEDICUS”, of the University of Patras"

Bioinspired Nanotrap for Nuclear Fuel Resource Mining from Ocean
Shengqian Ma
Department of Chemistry, University of North Texas, USA
Email: Shengqian.Ma@unt.edu
The long-term use of nuclear power for energy applications relies on the secure andeconomical supply of nuclear fuel. Among various natural sources of uranium for use in nuclear
reactors, sea water is highly appealing given that the oceans contain about 4.5 billion tons of
dissolved uranium, almost 1000-fold that estimated for mineral reserves. Nonetheless, theconcentration of uranium in seawater is extremely low (3–3.3 mg/L or 3–3.3 ppb); this, coupledwith the presence of relatively high concentration of other metal ions, makes uranium mining fromseawater a daunting challenge. Inspired by the features of metalloproteins for metal binding in
nature, a series of highly robust and water/chemical stable porous organic polymer (POP)-based
uranium “nanotraps” have been rationally designed and investigated for efficient and effective
uranium extraction from seawater.

Figure. Bio-inspired nanotrap for selective extraction of uranium from seawater.

[1] Q. Sun, B. Aguila, J. Perman, A. S. Ivanov, V. S. Bryantsev, L. Earl, C. Abney, L. Wojtas, S.
Ma, Nat. Commun. 9, 1644 (2018).
[2] Q. Sun, B. Aguila, L. Earl, C. Abney, L. Wojtas, P. K. Thallapally, S. Ma, Adv. Mater. 30,
1705479 (2018).
[3] Y. Song, C. Zhu, Q. Sun, B. Aguila, C. Abney, L. Wojtas, S. Ma, ACS Cent. Sci. 7, 1650-1656(2021).
[4] M. Hao, Z. Chen, X. Liu, X. Liu, J. Zhang, H. Yang, I. N. G. Waterhouse, X. Wang, S. Ma, CCS
Chemistry, 4, 2294-2307 (2022).

Electron delocalisation in switchable polynuclear Ni3 and Ni6complexes based on a triphenylene trisemiquinone bridge
T. Mallah,a* Y. Wang,a A. Colin,a F. Lambert,a N. Bridonneau,a E. Rivière,a R. Guillot,a Ch.
Herrero,a N. Suaud,b N. Guihéryb
Institut de Chimie Moléculaire et des Matériaux d’Orsay, Université Paris-Saclay, BâtimentHenri Moissan, 9100 Orsay, France, bLaboratoire de Chimie et Physique Quantique, UniversitéPaul Sabatier, 118 route de Narbonne 31062 Toulouse Cedex 09, France.
aE-mail : talal.mallah@universite-paris-saclay.fr

A trinuclear (Ni3) complex (Fig.1) is assembled from the reaction of Ni(II) capped witha blocking tris-pyrazolyl borate tridentate ligand and deprotonated tris-catecholatehexahydroxytriphenylene (H6HHTP).1 The crystal structure and the magnetic data areconsistent with a three-electron oxidized bridge leading to the tris-semiquinone form witha single electron. Electrochemistry data allows the reversible reduction of the central
ligand to the tris-catecholate form and one-electron oxidation accompanied by a change
in the magnetic behavior as evidenced by EPR (Fig. 2). EPR data show that the single
electron is rather delocalized over the three Ni(II) moieties in the pristine tris-semiquinone
form, while in the two-reduced species it is localized close to one Ni(II) ion. Wave function
based theoretical calculations give insights into the exchange coupling between thecentral radical and the metal ions .

Figure 1. Crystal structure, EPR and electrochemistry of the Ni 3 complex and crystal structure of Ni6.

[1] Wang, Y. T.; Lambert, F.; Riviere, E.; Guillot, R.; Herrero, C.; Tissot, A.; Halime, Z.; Mallah, T.
Electronic and spin delocalization in a switchable trinuclear triphenylene trisemiquinone bridged
Ni-3 complex. Chem. Commun. 2019, 55 (82), 12336-12339. DOI: 10.1039/c9cc05183j

Materials in Metastable Forms – molecules to metals
Mark W. Meisel
Department of Physics and the National High Magnetic Field Laboratory (or MagLab),
MagLab High B/T Facility, University of Florida, Gainesville, FL 32611-8440, USA
Email: meisel@ufl.edu
An intense effort is being made to synthesize new materials whose mechanical andelectrodynamical properties may possess the desired/targeted characteristics and/or allow their
behaviors to be tuned by external stimuli. Recent activities of three dramatically different
approaches will be discussed and the common themes present in these systems will behighlighted.
Firstly, the work being performed in collaboration with the STM (scanning tunnelling
microscopy) and STS (scanning tunnelling spectroscopy) team at Šafárik University in Košice,Slovakia, where external magnetic fields up to few tesla may be applied on samples cooled tonominally 5 K, with Fe(II) spin-crossover (SCO) samples provided by the Shatruk Group in
Chemistry at Florida State University in Tallahassee, will be presented. The local electronic
environment of the Fe(II) ion is a crucial aspect of this work [1].
Secondly, the results of a pure and compositionally tuned alloy, CrMnFeCoNi, whose
equiatomic composition is commonly referred to as Cantor alloy, one of the class of systems
known as high-entropy alloys possessing novel mechanical and electromagnetic properties.
Experimental and DFT (density functional theory) results are combined to indicate the overall
importance of the local microscopic volume, influenced by the compositional neighborhood, ingoverning the strength and interaction of a local magnetic spin [2].
Thirdly, the development and operation of the High BxT (magnetic field strength times
temperature) Facility at UF will be described as part of a project to demonstrate the scalability of
inductive heating synthesis/tempering of alloys in high magnetic fields. The results of growing
pure Co from a Co-S flux in fields up to 9 tesla will be described, since Co liquid was cooled to asolid while being in the ferromagnetic state. The main theme is that small changes in the freeenergy may lead to materials with new properties [3].
Aspects of this work were/are supported, in part, by the European Microkelvin Platform(EMP), for the STM/STS work at UPJŠ in Košice, the NSF via DMR-1708410, DMR-1852138,
DMR-1644779 and DMR-2128556 (MagLab), the State of Florida, and by DOE EERE AMO DEEE000913. The views expressed herein do not necessarily represent the views of the DOE or
any agency thereof.
[1] M. Gakiya-Teruya et al., J. Am. Chem. Soc. 143 (2021) 14563, doi.org/10.1021/jacs.1c04598[2] T.A. Elmslie et al., Phys. Rev. B 106 (2022) 014418, doi:10.1103/PhysRevB.106.014418,
and submitted arXiv:2208.09537.
[3] C.L.
Benyacko
et
al.,
Bull.
Am.
Phys.
Soc.
March
(2023)
D46.4,
https://meetings.aps.org/Meeting/MAR23/Session/D46.4.

New insights into the use of encapsulated atomic hydrogen in POSS
cages as spin qubit
G. Mitrikas
Institute of Nanoscience and Nanotechnology, NCSR Demokritos, Aghia Paraskevi Attikis,
15310 Athens, Greece
Email: g.mitrikas@inn.demokritos.gr
Encapsulated atomic hydrogen in octa-silsesquioxane (POSS) cages of the Si8O12R8 type (where
R is an organic group) is the simplest alternative stable system compared to the more expensive
paramagnetic endohedral fullerenes (N@C 60 or P@C60). Despite the exceptionally long spinlattice relaxation times T1 (reaching 120 s at T=5 K), the phase memory times, TM, are much
shorter and do not exceed 15 μs even at LHe temperatures. Our previous detailed studies on
systems with R=OSiMe3, R=OSiMe2H, and R=CH═CH2 revealed two major decoherence
mechanisms: first, the well-known nuclear spin diffusion and second, the methyl rotation oforganic groups R [1-4]. The later mechanism is responsible for the extreme shortening of T M toabout 1 μs at low temperatures (50 K < T < 150 K) which is a serious drawback for applicationsin spin-based quantum technologies.
Herein we extend our studies to the two smallest derivatives of the POSS family with R=CH3 and
R=H (Figure) as a benchmark for the effect of methyl group rotation on the phase memory time
TM. For R=H we find a modest and monotonic temperature dependence of T M, whereas, for
R=CH3 the typical “U-shaped” behavior is observed. Moreover, HYSCORE spectroscopy reveals
that the hyperfine coupling constants of the cage 29Si atoms are the largest among all studied
relevant species to date. Based on these spectroscopic findings, we consider possible
opportunities and pitfalls on the implementation of H@POSS as qubit in near future applications.

1

2

Figure. Structure of the two smallest POSS molecules studied in this work. 1, R=CH3. 2, R=H[1] G. Mitrikas, Phys. Chem. Chem. Phys., 2012, 14, 3782–3790.
[2] G. Mitrikas et al, Phys. Chem. Chem. Phys., 2014, 16, 2378–2383.
[3] G. Mitrikas and S. Menenakou, Phys. Chem. Chem. Phys., 2020, 22, 15751-15758.
[4] G. Mitrikas and R. Carmieli, J. Phys. Chem. C, 2021, 125, 9899−9907.

Spin State Switching in Crystals and Soft Matter
G. G. Morgan,a* C. T. Kelly,a S. Dunne,a I. A. Kühne,a A. Barker,a K. Esien,b S. Felton,b H.
Müller-Bunz,a Y. Ortin.aaSchool of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland

Centre for Nanostructured Media, School of Mathematics and Physics, Queen’s University
Belfast, BT7 1NN Belfast, Northern Irelandb

Email: grace.morgan@ucd.ie
Much effort has been expended in recent years to develop the materials assembly of spincrossover (SCO) complexes and impressive results have been achieved in stabilizing andisolating monodisperse nanoparticles, nanocrystals, thin films, micro- and nanopatterned media,
Langmuir-Blodgett surface mono- and multilayers and hysteretic soft media assemblies.1 We
have examined different methods to conserve the spin state switching we observe in many
crystalline samples with Mn(III) and Fe(III) complexes in soft matter environments. Here werationalize why thermal spin crossover has not yet been observed in soft matter forms of Mn(III)complexes, and contrast this with the behaviour of related Fe(III) complexes where spin stateswitching can be achieved in many material forms. In particular, we look at methods to achieve
spin state switching in soft matter forms with ferric iron and report here reversible proton-induced
spin state switching in solution in an Fe(III) complex at room temperature.2 Infrared spectroscopy
suggests a coordination-induced spin state switching (CISSS) effect, whereby protonation
displaces the metal-phenoxo donors. An analogous complex with a diethylamino group on theligand, was used to combine the magnetic change with a colorimetric response. Comparison of
the protonation responses of both complexes reveals that the magnetic switching is caused byperturbation of the immediate coordination sphere of the complex. These complexes constitute a
new class of analyte sensor which operate by magneto-modulation, and can also yield acolorimetric response.

Figure. (a) UV-visible absorption spectra for low spin Fe(III) with successive additions ofacid/base; (b) Plot of normalized extinction coefficient during an acid/base cycling experiment (c)ΧMT versus acid/base determined by NMR.
[1] P. N. Martinho, Y. Ortin, B. Gildea, C. Gandolfi, G. McKerr, B. O’Hagan, M. Albrecht and G.
G. Morgan, Dalton Trans., 2012, 41, 7461-7463[2] C. T. Kelly, S. Dunne, I. A. Kühne, A. Barker, K. Esien, S. Felton, H. Müller-Bunz, Y. Ortin, G.
G. Morgan, Angew. Chem. Int. Ed., 2023, 62, e202217388
Muralee Murugesu, Ottawa, CanadaA new generation of lanthanide-based Single-Molecule Magnets
M. Murugesu*
1

Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Canada,
K1N6N5.
E-mail: m.murugesu@uottawa.ca

Multimetallic rare-earth systems and especially DyIII, ErIII-based materials have sparked muchinterest in the area of molecular magnetism due to the large intrinsic magnetic anisotropy of thelanthanide ions. When such a unique property is combined with a high-spin ground state (S) in amolecular complex, it causes slow relaxation of the magnetization as seen for Single-Molecule
Magnets (SMMs). Lanthanide only SMMs are rare due to the difficulty in promoting the magnetic
interactions via the overlapping bridging ligand orbitals with the contracted 4f orbital of the ions.
Toward the goal of inducing significant magnetic interaction between lanthanide ions andsubsequently isolating high-energy barrier SMMs, our research has focused on the use ofphenoxide bridges as superexchange pathways between spin carriers. 1-3 In addition, radical
bridged complexes provides an alternative approach for inducing significant interactions between
the spin carriers.4 Such approach could ultimately allow efficient coupling of 4f ions and yield
SMMs with record breaking blocking temperatures.

Figure. Tetranuclear SMM with hysteresis with large coercive field.

[1] [1] P.-H., Lin; R. Clerac;* M. Murugesu,* and co-workers, Angew. Chem. Int. Ed., 2008, 47,
8848.
[2] F. Habib; M. Murugesu,* and co-workers, J. Am. Chem. Soc., 2011, 133, 8830.
[3] J. Long; M. Murugesu,* and co-workers, J. Am. Chem. Soc., 2011, 133, 5319.
[4] N. Mavragani; D. Errulat; D. A. Gálico; A. Kitos; A. Mansikkamäki; M. Murugesu* Angew.
Chem. Int. Ed., 2021, 60, 24206.

Probing electron densities and atom-by-atom vibrational spectra byatomic-resolution microscopy and theory reveal fascinating physics
Sokrates T, Pantelides
Department of Physics and Astronomy and Department of Electrical and Computer Engineering,
Vanderbilt University, Nashville, Tennessee 37235, U.S.A.
Email: pantelides@vanderbilt.edu
Scanning transmission electron microscopy (STEM) has undergone major revolutionary
advances in the last two decades, starting with sub-Angstrom spatial resolution in imaging
materials and structures, more recently the ability to image electric fields from which one derives
potential and electron distributions, and, even more recently, few-meV energy resolution inelectron-energy-loss spectroscopy (EELS) that enables vibrational spectroscopy. At the sametime, high-performance computers enable unprecedented levels of density-functional-theory
calculations that complement atomic-resolution STEM imaging and STEM/EELS of phonons in
crystals and nanostructures. The combination of experiments and theory provide mutual
validation of results and unveils fascinating new physics.
Working with several world-class STEM microscopists and materials scientists, my group has
provided the theoretical lynchpin in several major recent projects. The talk will cover the mostinteresting highlights of several projects – direct visualization of “anionic electrons” in an electride,a novel class of materials, revealing unexpected H traces with significant implications1; emergent
interface vibrational structure in oxide superlattices 2; direct visualization of localized vibrations at
a complex grain boundary3; single-atom vibrational spectroscopy with chemical-bond sensitivity
around Si impurities in graphene4; fascinating new discoveries in the behavior of water confinedin carbon nanotubes5; and mapping and analysis of phonons in hexagonal BN at hightemperatures, up to 1300 K.6
1.

2.

3.

4.

5.
6.

Q. Zheng, T. Feng, J. A. Hachtel, R. Ishikawa, Y.-Q. Cheng, L. Daemen, J. Xing, J.-C. Idrobo, J.-Q. Yan, N. Shibata,Y. Ikuhara, B. C. Sales, S. T. Pantelides, M. Chi, “Direct visualization of anionic electrons in an electride reveals
inhomogeneities”, Science Advances 7, eabe6819 (2021).
E. R. Hoglund, D.-L. Bao, A. O’Hara, S. Makarem, Z. T. Piontkowski, J. R. Matson, A. K. Yadav, R. C.
Haislmaier, R. Engel-Herbert, J. F. Ihlefeld, J. Ravichandran, R. Ramesh, J. D. Caldwell, T. E. Beechem, J. A.
Tomlo, J. A. Hachtel, S.T. Pantelides, P. E. Hopkins, J. M. Howe, “Emergent interface vibrational structure inoxide superlattices”, Nature 601, 556 (2022).
E. R. Hoglund, D.-L. Bao, A. O’Hara, T. W. Pfeifer, M. S. B. Hoque, S. Makarem, J. M. Howe, S. T. Pantelides,
P. E. Hopkins, J. A. Hachtel, “Direct visualization of localized vibrations at complex grain boundaries” Advanced
Materials 35, 2208920 (2023).
M. Xu, D.-L. Bao, A. Li, M. Gao, D. Meng, A. Li, S. Du, G. Su, S. J. Pennycook, S. T. Pantelides, and W. Zhou,“Single-atom vibrational spectroscopy with chemical-bond sensitivity”, Nature Materials 16 March 2023
https://doi.org/10.1038/s41563-023-01500-9
X. Jin, D.-L. Bao, X. Xu, A. Mazumdar, J. A. Hachtel, S. T. Pantelides, “Theory and spatially resolved vibrational
spectroscopy of water-filled carbon nanotubes” APS March meeting 2023
A. O’Hara, B. Plotkin-Swing, N. Dellby, J.-C. Idrobo, T. C. Lovejoy, and S. T. Pantelides, ”High-temperaturephonon dispersions and spectra at the nanometer scale by electron-energy-loss spectroscopy”, APS March
Meeting 2023.

The theory participants are group members De-Liang Bao, Andrew O’Hara, and Xin Jin.
The theoretical work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences,
Materials Science and Engineering Division grant DE-FG02-09ER46554 and by the McMinn Endowment at
Vanderbilt University.

Deliberate replacement of trivalent metal ions in a family of
pentanuclear {MIII4LnIII} (M = Fe, Cr, Ga; Ln = Gd, Dy, Y) heterometallic
clusters
K. N. Pantelis,* Th. C. Stamatatos
Chemistry Department, University of Patras, Patras 26504, Greece
Emails: kostaspantelis95@gmail.com (presenting author),
thstama@upatras.gr (corresponding author)
Heterometallic chemistry of 3d- and 4f-metal ions has attracted the interest of several
scientists working in the areas of coordination chemistry, molecular magnetism, optics, catalysis,
and materials science. The main interest stems from the ability of transition metals andlanthanides, when combined in the same molecular entity, to yield structurally beautiful
compounds with exciting magnetic properties, such as single-molecule magnets or molecularmagnetic refrigerants. Although numerous 3d/4f-metal cluster compounds have been reported todate, there is still a thirst for the synthesis of high-nuclearity, isoskeletal complexes, where the
3d-metal ion will be deliberately replaced in the polymetallic motif without breaking the core
structure but instead altering the physical (magnetic, optical, etc.) properties.[1] It thus seems
promising to combine highly anisotropic or isotropic lanthanide ions, e.g. DyIII (6H15/2 ground term)and GdIII (S=7/2), respectively, with different trivalent transition metal ions such as Cr III (S=3/2) or
high-spin FeIII (S=5/2), preferably interacted in a ferromagnetic way.[2] In order to study themagnetic contributions of the above spin carriers, we have extended the work by replacing either
CrIII and FeIII ions with diamagnetic GaIII centers or the DyIII and GdIII ions with diamagnetic YIII
centers. Herein, we report the synthesis, structures and magnetic properties of a family of
isoskeletal {M4Ln} clusters, where M = FeIII, CrIII, GaIII and Ln = GdIII, DyIII, YIII, which exhibits aunique ‘bat’-like topology (Figure 1), resulting from the use of N-salicylidene-2-amino-5chlorobenzoic acid (sacbH2) as a chelating/bridging ligand.
(a)

(b)

(c)

Figure 1. (a) The molecular structure of the isoskeletal {M4Ln} complexes. (b) The ‘bat’-likemetallic skeleton. (c) The chemical formula of the ligand sacbH2.
[1] D. I. Alexandropoulos, L. Cunha-Silva, G. Lorusso, M. Evangelisti, J. Tang, T. C. Stamatatos,
Chem. Commun., 2016, 52, 1693-1696.
[2] Y. Peng, M. K. Singh, V. Mereacre, C. E. Anson, G. Rajaraman, A. K. Powell, Chem. Sci.,
2019, 10, 5528-5538.

Molecular ordering of nanoconfined ionic liquids detected with T 2resolved diffusion NMR
M. Karagianni1, L. Gkoura2, G. Romanos1, N. Panopoulos1, A. Chatzichristos3, A. Srivastava3,
D. Homouz3, J. Hassan3, M. Fardis1, and G. Papavassiliou1*
1

Institute of Nanoscience & Nanotechnology, NCSR Demokritos, 15310 Agia Paraskevi, Attiki,
Greece.
2
Division of Science, New York University Abu Dhabi, Abu Dhabi, UAE.
3
Department of Physics, Khalifa University of Science and Technology, 127788 Abu Dhabi,
UAE.
Email: g.papavassiliou@inn.demokritos.gr

Molecular motion in nanosized channels can be highly complicated. For example, watermolecules in ultranarrow hydrophobic nanopores move rapidly and coherently in a single file,whereas by increasing the pore size they organize into coaxial tubes, displaying stratified
diffusion. Interestingly, an analogous complex motion is predicted in viscous charged fluids, suchas room temperature ionic liquids (RTILs) confined in nanoporous carbon or silica; however,experimental evidence is still pending. Here, by combining 1H NMR diffusion experiments indifferent relaxation windows with molecular dynamics simulations, we show that the imidazoliumbased RTIL [BMIM]+[TCM]−, entrapped in the MCM-41 silica nanopores, exhibits an intricate
dynamic molecular ordering; adsorbed RTIL molecules form a fluctuating charged layer near thepore walls, while in the bulk pore space they diffuse discretely in coaxial tubular shells, withmolecular mean square displacement following a nearly ∼τ0.5 time dependence, characteristic of
single file diffusion [1]. We will further show the pronounced similarities of this effect with watermolecules organization into ultranarrow carbon nanotubes.

Figure. Left Panel: RTIL in MCM-41 nanoporous silica diffuses in single file as shown by theexperimental (yellow circles) and theoretical simulations (orange color line) of the 1H NMR spinecho decay. Right Panel: Molecular Dynamics simulation of RTIL organization into a MCM-41
pore with size ⁓4 nm.
M. Karagianni et al., Communications Materials 4, 9 2023

Investigation of the cooperative Spin-Crossover in a mononuclear
manganese(III)-complex via solid-state NMR crystallography
Wassilios Papawassiliou1*, José P. Carvalho2, Georgios Papavassiliou3, Grace G. Morgan4 andGaël de Paëpe1
1 Univ. Grenoble Alpes, CEA, IRIG-MEM, Grenoble, France,
2 Interdisciplinary Nanoscience Center (iNANO) and Departament of Chemistry, Aarhus
University, Gustav Wieds Vej 14, DK-8000 Aarhus C, Denmark
3 Institute of Nanoscience and Nanotechnology, National Center for Scientific Research“Demokritos”, 153 10 Aghia Paraskevi, Attiki, Greece
4 School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland,
Email: wassilios.papawassiliou@cea.fr
Spin-Crossover (SCO) complexes are an emergent class of materials, defined by areversible transition between two electron spin states upon applying an external stimulus such astemperature, light or electric field, that are highly promising as multifunctional molecular switches.
To this date, despite all efforts, the way that changes in the coordination of individual atoms affectthe distribution of the electron spin density throughout the molecular complex remains obscure,hindering the understanding of the exact nature of the phase transition. Here, by employing highresolution variable-temperature paramagnetic solid-state NMR crystallography on the cooperative
SCO complex [MnL1]+PF6- [1], we succeeded to correlate the paramagnetic NMR shifts to thestructural and electronic changes that the Mn(III)-mononuclear complex is undergoing, and map
the electron spin density changes across the SCO transition upon cooling/heating at atomic scale.

Figure 1. Variable Temperature 1H LTMAS NMR spectra of the compound [MnL1]+PF6- .

[1] P. N. Martinho et al, “Cooperative spin transition in a mononuclear manganese(III) complex,”Angew. Chem. Int. Ed. 51, 12597–12601 (2012).

Polyurea-Crosslinked Biopolymer Aerogels as a Versatile Platform forthe Design and Synthesis of Nanostructured Materials forEnvironmental and Biomedical Applications
P. Paraskevopoulou
Inorganic Chemistry Laboratory, Department of Chemistry, National and Kapodistrian Universityof Athens, Panepistimiopolis Zografou 15771, Athens, Greece
Email: paraskevopoulou@chem.uoa.gr
Biopolymer aerogels are attractive materials because they: (a) come from renewable(natural) resources; (b) are prepared in water; (c) bear a large number of functional groups
available for coordination to metal ions, hydrogen bonding, functionalization etc.; (d) arebiocompatible, biodegradable and non-toxic; and, sometimes, (e) may be converted pyrolyticallyto carbon aerogels with ultra-high open porosities and surface areas. However, the maindrawback of most biopolymer aerogels is that they are mechanically weak materials. This issue
was rectified recently with the synthesis of polyurea-crosslinked biopolymer (X-biopolymer)
aerogels [1-2]. For example, X-M-alginate aerogels (Figure 1; M: divalent or trivalent cation) canbe as stiff as the best organic aerogels at half or one third of their density, and extremely stablein all aquatic environments with pH in the range of 3-9. These properties allow their application toenvironmental remediation, as adsorbents of heavy metals, or in biomedicine, as implants. In
addition, certain X-alginate aerogels can be pyrolyzed to metal- and N-doped carbon aerogels ingood yields, allowing for the synthesis of porous carbon electrodes and catalysts.

Figure 1. Polyurea-crosslinked M-alginate (X-M-alginate) aerogels (M: Ca, Co, Ni, Cu, Fe).
[1] P. Paraskevopoulou, I. Smirnova, T. Athamneh, M. Papastergiou, D. Chriti, G. Mali, T. Čendak,
M. Chatzichristidi, G. Raptopoulos, P. Gurikov, ACS Appl. Polym. Mater. 2020, 2, 1974.
[2] G. Raptopoulos, M. Papastergiou, D. Chriti, E. Effraimopoulou, T. Čendak, N. Samartzis, G.
Mali, T. Ioannides, P. Gurikov, I. Smirnova, P. Paraskevopoulou, Mater. Adv. 2021, 2, 2684.
Acknowledgements: Work carried out in the frame of the COST-Action "Advanced Engineeringof aeroGels for Environment and Life Sciences" (AERoGELS, ref. CA18125) funded by theEuropean Commission. Financial support from the Special Account of Research Grants of the
National and Kapodistrian University of Athens is gratefully acknowledged. Covestro AG is also
acknowledged for the generous supply of polyisocyanates.

Magnetic Archimedean Tessellations in Coordination Solids
Kasper S. Pedersen
Department of Chemistry, Technical University of Denmark, Kongens Lyngby, Denmark
Email: kastp@kemi.dtu.dk
The combination of moderate to strongly reducing metal ions and π-conjugated ditopic linkers
has proven to be a feasible approach to realize e.g. electrically conductive magnets and roomtemperature molecule-based magnets [1]. Hitherto, these approaches have narrowly focused on
the 3d transition metal ions. In this presentation, we will show how reducing p- and f-block metal
ions may be employed to activate ligand redox-activity in a family of magnetic 2D coordination
solids. Notably, the higher coordination numbers of the f-block ions result in a variety of structureswith 2D tessellations constructed from 5-fold nodes [2]. For instance, the assembly of trans[LnI2]+/0 (Ln = lanthanide) with closed-shell and open-shell aromatic amines leads to metal-organic
framework structures complying with the Archimedean tessellations (= tessellations made from
more than one type of polygon; see example in the figure below). These Archimedean tessellation
structures verge on quasicrystallinity, and our synthetic strategy may provide a route to elusive
quasiperiodic metal-organic frameworks. In this presentation, we will furthermore discuss themagnetic properties of these materials and discuss the prospects for frustrated behavior inmagnetic Archimedean tessellations.

Figure. Single-crystal X-ray structure of DyIIII2(bipy)3/2(bipy•–)1 highlighting the ideal snub square tiling
structure.

[1] See for instance: (a) Perlepe et al. Science 2020, 370, 587; (b) Pedersen et al. Nat. Chem.
2018, 10, 1056. [2] (a) Voigt et al. Nat. Commun. 2020, 11, 4705; (b) Chen et al. J. Am. Chem.
Soc. 2021, 143, 14041; (c) Chen et al. Chem. Commun. 2023, 59, 1609.

Molecular Lanthanide Complexes for Quantum Technologies
S. Piligkos
Department of Chemistry, University of Copenhagen, Denmark
Email: piligkos@chem.ku.dk
We have shown, in collaboration with many co-workers, that molecular Lanthanide-based
coordination complexes hold potential for use as physical supports for the implementation ofquantum bits and quantum gates in Quantum Information Technology devices. We studied thecoherent dynamics of electronic and nuclear spins in Yb(trensal) by pulsed magnetic resonanceexperiments on oriented single-crystals. The coupled electronic qubit-nuclear qudit nature of thissystem allowed to propose a scheme for intrinsic implementation of efficient quantum error
correction schemes. In further work, we investigate the multifrequency single crystal c.w.- andpulse EPR spectra of Gd(trensal), to characterise the energy spectrum and coherent
magnetisation dynamics of its 8S7/2 ground term.

Figure. Experimental and simulated angular dependence of the 5 K X-band c.w.-EPR spectrum of asingle crystal of Gd(trensal).

Crystallographic and magnetic properties of LiFeO 2 and LiFe5-xMnxO8 compounds
Vassilis Panagopoulos, Vassilis Psycharis, Yiannis Sanakis, and Michael Pissas,
Institute of Nanoscience and Nanotechnology, NCSR Demokritos, Aghia Paraskevi, Athens,
Greece

The crystal structure/microstructure characterization and the magnetic properties of LiFeO 2 and
LiFe5-xMnxO8 compounds are presented using powder x-ray diffraction magnetization andMossbauer spectroscopy measurements. The LiFeO 2 compounds appears in ordered anddisordered form, depending on the preparation conditions. The disordered form of LiFeO 2 displays
diffuse scattering both in x-ray and electron diffraction patterns, meaning short range ordering.
The Mossbauer spectra indicates a magnetic transition at around 90 K. The broad absorption
lines in the Mossbauer spectra indicate a glass-type magnetic state. The magnetically split
spectra were analyzed with two broad sextets, in agreement with the x-ray and electron diffraction
data. We reach the same conclusion from the analysis of specific heat measurements. The LiFe 5xMn xO 8 compound exists in two forms for low Mn content, depending on the preparation
conditions. Samples with disordered spinel structure were prepared by quenching the LiFe 5ooxMn xO 8 samples from 1100 C to liquid H2O. By prolonged annealing at 700 C, ordered LiFe 5xMn xO 8 samples are produced. All the disordered samples were Rietveld refined with a single
phase and resolution limited diffraction peaks (no size broadening). Rietveld refinements of thesamples annealed at 700oC, and x<0.3 revealed that are single phase materials, with ordered
crystal structure. The Li ordered domain size decreases with x. For x>0.2 phase separation isobserved. For significant values of, x>0.8, the peaks connected with Li ordering disappeared.
Room temperature Mossbauer data indicate that the Mn ions occupy the octahedral sites of thespinel structure.

Magnetic Ordering and SCMs from Ln(III)-radical complexes

K. E. Preuss

Department of Chemistry, University of Guelph, Guelph, ON N1G 2W1, Canada
Email: kpreuss@uoguelph.ca

Magnetic properties of molecule-based materials depend on both molecular andsupramolecular architectures. Magnetic ordering requires strong interaction between individual
magnetic moments of the molecular units. Many thiazyl heterocycles readily support a
paramagnetic oxidation state, with a wide window of redox stability, as well as imparting significant
spin-density at the periphery of the molecule, unencumbered by bulky substituents. As a result,thiazyl heterocycles, and their selenzyl analogs, are ideal building blocks for molecule-basedmaterials that exhibit interesting magnetic properties, including ordering and structural phases
transitions that are accompanied by changes in magnetic state. [1] Additionally, thiazyls andselenazyls can be used in the design of paramagnetic ligands, providing an opportunity toincrease the total magnetic moment, increase the total anisotropy of the magnetic properties, andmediate strong magnetic interaction between metal-ion moments via exchange coupling. Thus,thiazyl and selenazyl ligands have applications in the design of single molecule magnets(SMMs)[2] and single-chain magnets (SCMs).
New results, including unpublished SCMs, will be disclosed. These results highlight the manydifferent ways in which paramagnetic thiazyls can be used to design materials that exhibit
magnetic memory.

[1] M. B. Mills, T. Wohlhauser, B. Stein, W. R. Verduyn, E. Song, P. Dechambenoit, M. Rouzières,R. Clérac, K. E. Preuss, J. Am. Chem. Soc. 2018, 140, 16904.
[2] C. A. Michalowicz, M. B. Mills, E. Song, D. V. Soldatov, P. D. Boyle, M. Rouzières, R. Clérac,K. E. Preuss, Dalton Trans. 2019, 48, 4514.

Structure-Superstructure interrelations in non-molecular crystal
structures based on cation arrangement
Vassilis Psycharis 1,*, Manolis Chatzigeorgiou1, Marios Katsiotis2
1

Institute of Nanoscience and Nanotechnology, National Center for Scientific Research“Demokritos” 15310 Athens, Greece; 2Group Innovation & Technology, TITAN Cement S.A.,111
43 Athens, Greece;
Email: v.psycharis@inn.demokritos.gr
The description of the structures based on polyhedra of anions is the traditional point of viewused by Pauling and is based on the idea that the "small" cations occupy positions in the voids
left in crystal structures by the larger atoms of anions such as oxygens [1]. A new approach has
been introduced by O’Keefe & Hyde [2a, b], where the role of ions is reversed i.e. the structure
description is based on the packing of cations and the anions are inserted at interstitial sites
among them. This new approach at the beginning, it was considered as purely geometric and nobonding type considerations were implied for the atoms involved in the packing within a crystal
structure. But recently in addition to the achieved simplifications in the presentation of many
structures the role of cations is reconsidered, as the packing of cations observed within the ionic
structures resemples that observed in their parent metal structures [3]. More interestingly, basedon the pioneering work in this field by O’Keeffe & Hyde [2c], it is found that in ternary oxides withtwo different metals the packing of cations corresponds to the packing of binary alloys. So, in thecase of β-Ca2SiO4 the packing of cations resembles to that of Ni2In prototype structure (B8b,
Strukturhericht designations). These observations have made the authors O’Keefe & Hyde tocharacterize oxides as “stuffed alloys”. In a recent work [4], the ideas developed in the work ofBarbier & Hyde [3] and O’ Keeffe & Hyde [2a] were applied in a systematic way for the study ofall belite polymorphs and the revealed structure-superstructure interrelations indicate that the
crystal structure description of inorganic compounds on the basis of their cationic building blocks
could be a very useful tool. Examples of other families of compound where this new approach inpresenting crystal structures is implemented will also be discussed.

[1] Pauling L. The Nature of the Chemical bond and the Structure of Molecules and Crystals:
3rd Edition, New York Cornell University Press, Ithaka, USA, 1960; pp 505[2] a O’Keeffe, M. & Hyde, B.G., 1985, 61, 77-144; b Vegas, Crystallography Reviews, 2000, 7,
189-283; c Vegas & A.; Mattesini, M., Acta Cryst. , 2010, B66, 338-344[3] Barbier, J.; Hyde, B.G., Acta Cryst., 1985, B41, 383-390[4] V. Psycharis, M Chatzigeorgiou, D. Koumbouri, M. Beazi-Katsioti, M. Katsiotis,
Crystals 2022, 12(12), 1692
Acknowledgments: This research was supported by NCSR ‘Demokritos’ Industrial Research
Fellowship Program [E.E.‐12149], funded by the Stavros Niarchos Foundation and TITAN
Cement S.A.

Heterometallic Cu/Ln complexes based on cubane subunits:
synthesis, molecular and intermolecular structure studies
D. Dermitzaki, M. Pissas, V. Psycharis and C. P. Raptopoulou*
Institute of Nanoscience and Nanotechnology, NCSR "Demokritos", 15310, Aghia Paraskevi,
Attikis, GREECE
Email: *c.raptopoulou@inn.demokritos.gr
A cubane-type subunit is an arrangement of atoms in a molecular structure that forms a cube,
and in the idealized case all vertices are symmetrically equivalent possessing Oh symmetry. The
cubane subunit is found in organic compounds, such as hydrocarbon cubane, C 8H8 and its
substituted derivatives, in inorganic compounds, such as SeCl4 and TeCl4, in coordination
compounds, such as [CoO(O2CMe)py]4 and as part of more complex structures, and also in
biological systems in the active sites of proteins and enzymes, e.g. [Fe 4S4] clusters, [Mn3CaO4]
subunit of the OEC in PSII, etc [1-3]. Reactions of copper carboxylato sources with the Schiffbase ligands o-OH-C6H4-CH-N(R)(CH2OH)2 (R = CH3, H3L1; C2H5, H3L2; CH2OH, H4L3) andlanthanide salts gave families of heterometallic Cu/Ln clusters with general formula[Cu5Ln2(L1,2)2(HL1,2)2(NO3)x(O2CR)y] (x+y=6, R = But, Pet), {Cu5Ln2}, [Cu4Ln3(OH)(NO3)2(HL3)2(H2L3)2(O2CR)5] (R = Pet), {Cu4Ln3}, [Cu6Ln4(OH)4(CO3)(NO3)(H2L3)6(O2CR)5(H2O)6] (R =But), {Cu6Ln4}, and [Cu8Ln4(OH)10(H2L3)6(O2CR)4(H2O)2] (R = Pet), and metal core topologies
based on [Cu3LnO4] or [Cu2Ln2O4] cubane subunits. The structural characteristics of all familiesof clusters, their lattice structures based on intermolecular interactions studied by Hirshfeld
Surface analysis methods, and preliminary magnetic studies are discussed.

Figure. The cubane subunits and the metal cores of the complexes discussed.

[1] L.Wang, X.Zheng, T.B.Kouznetsova, T.Yen, T.Ouchi, C.L.Brown, S.L.Craig, J.Am.Chem.Soc.
2022, 144, 22865-22869.
[2] A.E.Boncella, E.R.Sabo, R.M.Santore, J.Carter, J.Whalen, J.D.Hudspeth, C.N.Morrison,
Coord.Chem.Rev. 2022, 435, 214229.
[3] Y.Umera, K.Kawakami, J.-R.Shen, N.Kamiya, Nature 2011, 473, 55-60

The magnetic properties of heterometallic clusters based on an
asymmetric [Fe3+-Ln3+-Fe3+] (Ln = Gd, Tb, Dy, Ho) structural core.
Y. Sanakis,*,1 M. Savva,2 D. I. Alexandropoulos,2 M. Pissas,2 S. P. Perlepes,3 C.
Papatriantafyllopoulou,4 A. J. Tasiopoulos2

1

Institute of Nanoscience and Nanotechnology, NCSR Demokritos, Greece; 2Department ofChemistry, University of Cyprus, Cyprus; 3Department of Chemistry, University of Patras,
Greece; 4School of Chemistry, National University of Ireland Galway, Ireland.
Email: i.sanakis@inn.demokritos.gr

The compounds 1/Ln of the new trinuclear heterometallic Fe3+/Ln3+ family,[Fe2Ln(PhCO2)3((py)2CO2)((py)2C(OMe)O)2(NO3)Cl] (Ln = Gd (1/Gd), Tb (1/Tb), Dy (1/Dy), andHo (1/Ho)), where (py)2CO22- and (py)2C(OMe)O- are the anions of the gem-diol and hemiketal
derivatives of di-2-pyridyl ketone are based on an asymmetric “V-shaped” [Fe3+(μ-OR)Ln(μOR)2Fe3+]6+ structural core formed from the connection of the two terminal Fe3+ centers to thecentral Ln3+ ion either through one or two alkoxide. Direct current magnetic susceptibility studies
reveal the presence of weak antiferromagnetic interactions between the Fe3+ ions. Alternating
current magnetic studies indicate the presence of slow-magnetic relaxation in 1/Dy. The
electronic, magnetic and relaxation properties of the complexes were further monitored byvariable temperature 57Fe Mössbauer Spectroscopy. At T>80 K the spectra from the complexes
comprise two quadrupole doublets the hyperfine parameters of which reflect the distinct
coordination environment of the two Fe3+ terminal sites. At T<20 K, the Mössbauer spectra for
1/Dy are affected by magnetic relaxation effects. At 1.5 K, the spectrum of 1/Dy comprises welldefined magnetic sextets indicating relaxation times slower than the characteristic time of the
Mössbauer technique (10-7 s) in agreement with the dynamic magnetic measurements. 1/Gd
exhibits broad unresolved magnetic sextets at 1.5 K indicating that the spin relaxation time is of
the order of the Mössbauer characteristic time at this temperature. For 1/Tb, 1/Ho the Mössbauer
spectra exhibit slight broadening even at the lowest available temperature consistent withmagnetic relaxation times less than 10-7 s.

[1] M. Savva, D. I. Alexandropoulos, M. Pissas, S. P. Perlepes, C. Papatriantafyllopoulou, Y.
Sanakis, A. J. Tasiopoulos Dalton Trans. 10.1039/D2DT03938A in press

Toroidal magnetic molecules stripped to their basics
J. Schnack
Faculty of Physics, Bielefeld University, Bielefeld, Germany
Email: jschnack@uni-bielefeld.de
Molecular magnetic toroidal moments are molecule-based structures of quantum spins thatare expected to boost magnetic storage technology and quantum computing. We study selected
fictitious but typical examples of single-molecule toroidal magnet behavior, discuss the essenceof the concept, and clarify inappropriate or even wrong assignments of physical properties.
The first part of the presentation concerns the use of toroidal magnetic molecules as storage
bits [1]. Here I demonstrate that such molecules unavoidable possess a tunneling gap if their total
spin is integer (non Kramers).
The second part deals with the use as q-bits and addresses the decoherence properties if
the toroidal magnetic molecule is immersed in a spin bath [2]. We find no positive correlation
between the toroidal moment and long decoherence times. By accident we discovered special
scenarios with astonishingly long decoherence times.

Figure: Canted arrangement of anisotropy axes (yellow) in a triangular spin system (l.h.s.). Example
of decoherence measured via the decay of off-diagonal matrix elements of a reduced density matrix.
One particular superposition (ocher) of eigenstates of the canted system proves to be especiallystable over long times (r.h.s.).

[1] D. Pister, K. Irländer, D. Westerbeck, J. Schnack, Toroidal magnetic molecules stripped totheir basics, Phys. Rev. Research, 2022, 4, 033221.
[2] K. Irländer, J. Schnack, Studies of decoherence in strongly anisotropic spin triangles withtoroidal or general non-collinear easy axes, Phys. Rev. Research, 2023, 5, 013192.

Chiral Schiff base Zn(II) complexes: synthesis, characterization andDNA-interaction studies
K Stamatis1,2*, CP Raptopoulou1, C Dendrinou-Samara2, V Psycharis1
1

Institute of Nanoscience and Nanotechnology, National Centre for Scientific Research“Demokritos”, 15310 Aghia Paraskevi, Attikis, Greece
2
Inorganic Chemistry Lab, Chemistry Department, Aristotle University of Thessaloniki, 54124
Thessaloniki, Greece
Email: konstamat21@gmail.com
Zinc has a prominent role for various functions of the human body and the Schiff bases derivatives
show a variety of pharmacological applications [1]. Thus, novel neutral mononuclear enantiopureZn (II) complexes were synthesized by tetradentate chiral Schiff base ligands. The structures of
the complexes were determined by Single Crystal X-ray Diffraction and the complexes werecharacterized by Infrared spectroscopy (IR), 1H Nuclear Magnetic Resonance (1H NMR),
Ultraviolet-Visible spectroscopy (UV-Vis) and fluorescence spectroscopy. The circular dichroism
spectroscopy (CD) confirmed that the chirality was transferred by the ligands to the complexes.
The biological activity of the complexes was evaluated by the interaction studies with calf-thymous
DNA (CT DNA) through UV-Vis spectroscopy, viscosity, competitive studies with ethidium
bromide (EB) and CD studies. The results of the aforementioned measurements indicated thatthe complexes showed an affinity to bind to DNA with partial intercalation.

Figure. Molecular structure of chiral Schiff base Zinc (II) complex.

[1] Gurusamy, S., Krishnaveni, K., Sankarganesh, M., Nandini Asha, R., & Mathavan, A. Journalof Molecular Liquids, 345 (2022) 117045.

Mn3+ Spin Crossover Complexes: A Structural and Spectroscopic
Study
A. Sultan,a* I. A. Kuhne,a,b K. Esien,d H. Muller-Bunz,a S. Felton,d A. Ozarowski,c,eS. Hill,c,e G. G. MorganaaSchool of Chemistry, University College Dublin, Belfield, Dublin 4 IRELAND
FZU-Institute of Physics-Czech Academy of Sciences,Na Slovance 1999/2, Prague,CzechiacNational High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310
dSchool of Mathematics and Physics, Queen’s University Belfast, Belfast, UKe
Department of Physics, Florida State University Tallahassee, Florida 32310, USA
Email: aizuddin.sultan@ucdconnect.iebSpectroscopic, structural, and magnetic data on different types of Mn 3+ spin-crossovercomplex with Schiff base ligands will be presented. For example, the prevalence of chiral
crystallization of the [4-OMeSal2323]+ complex cation in different lattices will be examined.
Complexes of [Mn(4-OMe-Sal2323]X where X= ClO4- (1), BF4- (2), NO3- (3), Br-(4) and I- (5),crystallized in the chiral orthorhombic space group P21212 and the chirality in (methanol) solution
was confirmed via circular dichroism (CD) spectroscopy on single-crystals of high-spin complex(1) at room temperature, each measurement recorded on a solution of one crystal, Figure 1. [1]This revealed a 2:1 ratio of enantiomers in the chiral conglomerate, and solution CD
measurements on the same sample in methanol to show that it is stable toward racemization.
Solid-state UV-vis absorption spectra on high-spin complex (1) and mixed S=1/S=2 sample (5)reveal different intensities at higher energies, in line with the different electronic composition. The
statistical prevalence of the homochiral crystallization of [Mn(4-OMe-Sal2323)]+ in five lattices withdifferent achiral counterions suggests that the chirality may be directed by the 4-OMe-Sal2323
ligand, which could be useful in combining the functions of SCO and chirality.[2] Complexes
measured by SQUID magnetometry on polycrystalline samples revealed a range of thermal
evolution profiles in the solid state with stepped crossovers in complexes (3) and (5).

Figure 1. CD spectra comparison of delta and lambda enantiomers of [4-OMeSal2323]+.

[1] Gildea, B.; Harris, M. M.; Gavin, L. C.; Murray, C. A.; Ortin, Y.; Muller-Bunz, H.; Harding, C. J.;
Lan, Y.; Powell, A.K.; Morgan, G. G. Inorg. Chem., 2014, 53 (12), 6022-6033.
[2] Qin, L.-F.; Pang, C.-Y.; Han, W.-K.; Zhang, F.-L.; Tian, L.; Gu, Z.-G.; Ren, X.; Li, Z. Dalton
Trans., 2016, 45, 7340-7348

How Interfaces Influence Phase Transformations in
Layered Magnets, Hybrid Perovskites and Related Materials
Daniel R. Talham
Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 USA
Email: talham@chem.ufl.edu
Layered solids play prominent roles in several areas of materials science. Historically, they aremodel systems for our understanding of low dimensional magnetism and provided paradigm
changes in superconductivity. More recently, layered solids are often the precursors to exfoliatedsingle layer 2D materials of high interest for their exotic electrical, optical, mechanical and thermal
properties. Layered solids also feature in current lithium electrode technologies and are among
the most widely explored for future solutions. As for all mesoscale and nanoscale solids, highsurface-to-volume ratios can alter solid-state properties as surfaces play enhanced roles indetermining structure. However, these effects can be magnified in layered solids due to highly
anisotropic bonding and associated elastic properties. Our lab recently showed how solid-statephases of hybrid organic/inorganic layered solids can be switched, simply by altering theenvironment around preformed particles. Changes in surface environment alter the surface
energy (more specifically the surface stress) leading to changes of the effective internal pressure
on the particles. As the layered materials are more compressible perpendicular to the layers, thepressure changes can significantly alter the interlayer regions. This presentation will highlightexamples of using the particle interface to vary the effective internal pressure of layered solids,
leading to changes in structure, properties and reactivity. Examples will be drawn from organicinorganic hybrid perovskites, layered metal phosphonates and layered phosphates, illustrating
how control over the solid-liquid interface leads to reversible solid state phase transitions,switchable optoelectronic properties and changing intercalation chemistry.

Figure. Properties of the hybrid layered perovskite (C6H13NH3)2CuCl4 and the layered intercalation host
VOPO4·2H2O change dramatically in suspending solvents due to changing surface energy.

Fine Tuning the Hydrophobicity of a New Cu 2+ 3-Dimensional MOF
Through Single - Crystal Coordinating Ligand Exchange
Transformations
A. J. Tasiopoulos*,a, N. Panagiotou,a M. J. Manos,b D. L. Giokas,babDepartment of Chemistry, University of Cyprus, 1678 Nicosia, Cyprus.
Department of Chemistry, University of Ioannina, 45110 Ioannina, GreeceEmail:atasio@ucy.ac.cy

Our group has been investigating single-crystal to single-crystal (SCSC) transformation
reactions of a series of MOFs targeting to fine tune their properties. For example, a series ofSingle Crystal Coordinating Ligand Exchange (SCCLE) transformations were investigated in two
families of lanthanide MOFs and in particular in [Ln 2(NBDC)3(DMF)4] (H2NBDC = 2-amino-1,4benzene dicarboxylic acid) (Ln-NBDC), and [Ln2(CIP)2(DMF)2(H2O)2] (H3CIP = 5-(4carboxybenzylideneamino)isophthalic acid) (Ln 3+ = Nd3+, Eu3+, Gd3+,Tb3+) (UCY-2 and UCY-8 –10). [1,2] These modifications led to a significant amplification of the Eu3+ emission signals (forthe Eu3+ analogues), lifetimes and quantum yields compared to those of the as-prepared MOFs.
More recently the mixed metal Eu0.05Tb0.95-NBDC analogue of Ln-NBDC was employed toinvestigate the effect of controlled structural modifications through SCCLE transformations on thethermometric properties of luminescent MOFs. [3]Herein we report a new Cu2+ 3-dimensional MOF [Cu6(μ3-ΟΗ)3(ΑΙΡ)4(HΑΙΡ)]n·6nDMF·nH2O(1) (H2ΑΙΡ = 5-Aminoisophthalic acid) based on a tetranuclear butterfly – like secondary building
unit. It exhibits a microporous structure and a capability to exchange not only its DMF guest
molecules with bulky aromatic molecules but also its bridging μ3-OΗ- anions by CnH2n+1O- groups(n = 1 – 7) in a SCSC fashion. In fact, this is an unusual example of SCSC transformations
involving modifications in the monoatomic bridges of the structural core of the SBU of a MOF.
Interestingly, these transformations (and others involving bulkier alcohols that we were unable tocharacterize crystallographically) led to a significant increase of the hydrophobicity of the MOF
and to materials that could be potentially used in the removal of hydrophobic pollutants from
aqueous media.
References[1] M. J. Manos, E. J. Kyprianidou, G. S. Papaefstathiou, A. J. Tasiopoulos, Inorg. Chem., 2012,
51, 6308-6314.
[2] E. J. Kyprianidou, T. Lazarides, S. Kaziannis, C. Kosmidis, G. Itskos, M. J. Manos, A. J.
Tasiopoulos, J. Mater. Chem. A, 2014, 2, 5258-5266.
[3] A. Kourtellaris, W. Lafargue-Dit-Hauret, F. Massuyeau, C. Latouche, A. J. Tasiopoulos, H.
Serier-Brault, Adv. Opt. Mater. 2022, 10, 2200484
Acknowledgement
This work was supported by the Cyprus Research and Innovation Foundation Research Grant"EXCELLENCE/1216/0076" which is co-funded by the Republic of Cyprus and the European
Regional Development Fund.

η6-phenoxide 1st row transition metal complexes in unusual
geometries.
Nikolaos. Tsoureas,* and Ioannis Vagiakos

National and Kapodistrian University of Athens, Department of Chemistry, Inorganic Chemistry
Laboratory, Panepistimioupoli Zografou, Athens, 15784, Greece
Email: ntsoureas@chem.uoa.gr

First row transition metal complexes have attracted significant interest in applications likecatalysis, energy and magnetism. This is due to their smaller cost and their extensive redox
repertoire.
Recent efforts in our laboratory with bis-phenoxide ligands have furnished in good to
excellent yields organometallic first row-transition metal complexes in unusual geometries, as aresult of the ligand tailoring enforcing ηx (x = 1,6) coordination of the central arene ligand (Figure1). Initial structural and spectroscopic investigations suggest that the ligand is redox non-innocent
partially evidenced by the loss of planarity of the central arene ring upon traversing the series of
1st row transition metals (Cr, Fe, Co, Ni). Furthermore, cyclic voltammetry studies point to a richredox behavior which is currently under investigation.

Figure 1. Synthesis of bis-phenoxide arene complexes in unusual geometries.

In Quest of Controllable Electron Transfer Aimed to
Performance Optimization of Molecular Quantum Cellular Automata
Boris Tsukerblat,1,2* Shmuel Zilberg,2 Andrew Palii 2
1

Chemistry Department, Ben-Gurion University of the Negev, Beer-Sheva, Israel
Department of Chemical Sciences, Materials Research Center, Ariel University, Israel
3
Institute of Problems of Chemical Physics, Chernogolovka, Moscow Region, RF
Email: tsuker@bgu.ac.il

2

Here we give a short overview of the problem of Quantum Cellular Automata (QCA) as thebasis for molecular electronics employing nanometer-scale logic gates with ultra-high device
densities operating at high switching speed and room-temperatures, consuming extremely small
amounts of electrical power and small heat release. In molecular QCA circuits the binary
information is encoded in charge configuration of molecular mixed-valence cells. We describe thekey interactions determining the action of the cell in molecular gates and circuits such as
intramolecular electron transfer, vibronic coupling and Coulomb interactions within moleculararchitecture. We demonstrate that the strongly non-linear cell-cell response function required forthe efficient encoding and operating with the binary information crucially depends on these maininteractions. Then we show how the approach based on high level ab initio calculations combinedwith the parametric theory can shed light on the physical nature of different parameters thus

Figure. Potential surfaces in qQ-space for the compounds I, II, III and contour plots evaluatedwith the vibronic parameters and vibrational frequencies obtained through quantum-chemical
calculations.
approaching the goal of rational design of mixed valence cells. In the framework of the vibronicbi-orbital two-mode model [1] we consider controllable electron transfer and degree of localizationin mixed-valence oxidized norbornadiene C7H8 (I) and its polycyclic derivatives, C12H12 (II), C17H16,(III), C27H24 (IV), C32H28 (V) with two C=C chromophores. The model involves the modes localized
at the redox sites (“breathing“ mode q) and the inter-site vibration (Q) modulating the distances
between the redox fragments [2] (adiabatic picture of electron transfer is given in Figure).
A.P. thanks the Ministry of Science and Higher Education of RF for financial support (state assignment no.
AAAA-A19-119092390079-8).
[1] S. Zilberg, Y. Stekolshik, A. Palii, B. Tsukerblat, J. Phys. Chem. A 2022, 126, 2855.
[2] A. Palii, S. Aldoshin, S. Zilberg, B. Tsukerblat, Phys.Chem.Chem.Phys. 2020, 22, 25982.
Mark Turnbull, Massachusetts, USA

Low-dimensional Cu(II) magnetic lattices
Raquel Rodríguez Pérez,a Christopher P. Landee,b Louise N. Dawe,c Mercè Deumal,a Diane A.
Dickie,d Hannes Kühnee
and Mark M. Turnbull*,ba

Dept. Ciència de Materials i Química Física, & IQCTUB, Universitat de Barcelona, Martí i
Franquès 1, Barcelona, E-08028 Spain b Dept. of Physics, and Carlson School of Chemistry
and Biochemistry, Clark University, 950 Main St., Worcester MA 01610, USA. cDept. ofChemistry and Biochemistry, Wilfrid Laurier University, Waterloo, Ontario, Canada. d Dept. ofChemistry, University of Virginia, Charlottesville, VA, 22904 USA. eHelmholtz-Zentrum DresdenRossendorf, Bautzner Landstraße 400 - 01328 Dresden, Germany
Email: mturnbull@clarku.edu
Low-dimensional magnetic lattices provide a rich playground for the study of magnetismand magnetostructural correlations. The magnetic properties are determined by the orientationof magnetic species in the crystalline lattice and local anisotropy/geometry, as well as exchange
and superexchange pathways. Although one normally can normally use the crystal lattice as a
guide to the magnetic lattice, our understanding of the magnetostructural relationships is stilldeveloping and there are many examples where preliminary expectations based on the crystal
lattice prove to have been misleading. Two examples will be presented including a 2Dferromagnetic layer where the analysis of the magnetic properties led to a revised
understanding of the crystal structure (Figure 1) and a 2D-system with XY-anisotropy based on
Cu(II) [1].

Figure 1 – [Cu(pzdo)2(H2O)2](NO3)2[1] Opherden, D.; Tepaske, M.S.J.; Bärtl, F.; Weber, M.; Turnbull, M.M.; Lancaster, T.; Blundell,
S.J.; Baenitz, M.; Wosnitza, J.; Landee, C.P.; Moessner, R.; Luitz, D.J.; Kühne, H. Phys. Rev.
Lett. 2023, 130, 086704(1-6).

Colloidal nanoparticles, liquid phase synthesis, characterization andtheir applications
Vasileios Tzitzios
Institute of Nanoscience and Nanotechnology, NCSR “Demokritos” 15310, Athens, Greece
v.tzitzios@inn.demokritos.gr
Solution-based methods are enable to produce a large variety of compounds at relatively
low-temperatures with precise compositions, structures and morphologies.
Using this low-temperature solution-based approach various compounds can be readily
accessed; e.g., metal, metal oxides and alloys. The method based on the thermolytic
decomposition/reduction of inorganic metal salts in a solvent-free aliphatic amine mixture. Our
subsequent work showed that this approach can be significantly expanded to include also metal
phosphides and ternary systems with a variety of compositions and accessible crystal structures.
Furthermore, the synthetic process can be modified to produce materials with controlled
nanostructure and morphology. Summarizing, we are presenting here a generalized solutionbased approach for synthesis of morphologically diverse nanomaterials, including
superparamagnetic Fe3O4, ferromagnetic L10 ordered FePt and CoPt nanoalloys, as well astransition metal phosphides and carbides.

Intensity (a. u.)(a)
H2SO4 treateduntreated

20

25

30

35

40

45

50

55

60

5

2 (degree)

Magnetization (emu/g)

40

(b)

20

0

-20

-40
-30

untreated
H2SO4 treated
-20

-10

0

10

20

30

Magnetic Field (kOe)

Figure 1. TEM image, elemental mapping, XRD pattern and RT magnetic hysteresis loop of L1 0 ordered
FePtBi nanoalloys.

Synthesis and characterisation of Spin Crossover nanoparticles ofFe(II) with 4-Amino-1, 2, 4- triazole ligand
Efstathia Voudouri,1 Nikolia Lalioti,*1 Alexander Charitos,1 John Parthenios,2 Ondrej Malina,3Vassilis Tangoulis1
1

Department of Chemistry, Laboratory of Inorganic Chemistry, University of Patras, 26504,
Patras, Greece.
2
Institute of Chemical Engineering Sciences, Foundation of Research and Technology-Hellas(FORTH/ICE-HT), Stadiou Street, Platani, Patras, 26504 Greece
3
Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology
and Research Institute (CATRIN), Palacký University Olomouc, Křížkovského 511/8, 77900,
Czech Republic.
Email: lali@upatras.gr
The SCO phenomenon in molecular complexes and transition metal ion-coordination
polymers (CPs) is a topic of long-term interest of inorganic chemistry and materials science ingeneral. In recent years, significant advances have been made in the synthesis of nano-SCO
materials in a variety of forms, such as nano-particles, thin membranes, nano-motifs, nanoheterostructures and nano-composite materials, with increasing emphasis on the exploration of
nano-devices of this spectacular phenomenon. A particularly interesting family of iron(II) CPs is
the one-dimensional (1D) coordination polymer of Fe(II), with general formula {[Fe(Rtrz) 3]X2}nRtrz = substituted triazole, X = monovalent anion, which has collected a number of remarkablestudies in the solid state.
We will discuss the nano-synthesis and characterization of 1-D SCO
NPs [Fe(NH2trz)3]Χ⋅3H2O (NH2trz=4-Amino-1, 2, 4-triazole, Χ=BF4, Br) using the reverse micellar
synthetic method where we used the non-ionic TX100 as surfactant. The structure, morphology,
magnetic and thermodynamic properties of the synthesized SCO NPs were explored using
electron microscopy (TEM), X-ray diffraction (pXRD), superconducting quantum interference
magnetometer (SQUID), UV-Vis and infrared FT-IR spectroscopy, and calorimetry (DSC). To
study the system more thoroughly, we applied different doping protocols a) of the ligand with 1H1, 2, 4-triazole and b) of divalent iron with divalent copper[1].

[1] N. Lalioti, E. Giannopoulou, A. Charitos, J. Parthenios, O. Malina, M. Polaskova, A. Kalarakis,
V. Tangoulis, Dalton Trans., 2023, 52, 2937.

Magnetism of Molecular Compounds and a Haldane MOF Revealed by
Advanced Spectroscopies

Ziling (Ben) Xue
Department of Chemistry, University of Tennessee-Knoxville, TN 37996, USA
Email: xue@utk.edu

This talk will focus on our recent studies of single-molecule magnets (SMMs), intermolecularmagnetic interactions, and a 2D Haldane MOF (metal-organic framework) by far-IR and Raman
magneto-spectroscopies (FIRMS and RaMS), inelastic neutron scattering (INS), and high-field
EPR (HFEPR). For SMMs, zero-field splittings (ZFS) in d-metal complexes and intra-manifold
separations in f-metal complexes lead to barriers for their magnetic relaxations. We havesuccessfully used the spectroscopies to determine large separations in several SMMs.1-5 The
spectroscopies also reveal rarely observed spin-phonon couplings in the molecular compounds.
For the topological material, we have found that a 2D Ni(II) MOF possesses a Haldane gap.

1.
2.
3.
4.
5.

D. H. Moseley et al. Nat. Comm., 2018, 9, 2572.
S. E. Stavretis et al. Eur. J. Inorg. Chem., 2019, 1119.
S. E. Stavretis et al. Chem. Eur. J., 2019, 25, 15846.
D. H. Moseley et al. Inorg. Chem., 2020, 59, 5218.
D. H. Moseley et al. Inorg. Chem., 2022, 61, 17123.

Molecular Spin Qubits for Quantum Computer and High-Density
Memory Devices Based on Molecular Magnets
Masahiro Yamashita
Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-Ku, Sendai 9808578, Japan
Email: yamasita@agnus.chem.tohoku.ac.jp
Spintronics, based on the freedoms of charge and spin of the electron, is a key technology
in the 21st century. Magnetic random access memory (MRAM), which uses giant
magnetoresistance (GMR), has several advantages
compared with electronics. Although conventional
magnets composed of transition metals are normallyused, in our study, we use single-molecule magnets(SMMs) to overcome “Moore`s Limitation”. SMMs
are also available for quantum computer. I will talkabout the molecular spin qubits for quantum
computer as well as high-density memory devices
such as single-molecule memory device, SMMs
encapsulated into SWCNT, and metallic conducting
SMMs with negative magnetoresistances.
As for molecular spin qubits for quantum
computer, we must increase T1 (spin-lattice
relaxation time) and T2 (spin-spin relaxation time).
Therefore, we will focus on the following threestrategies:(1) Crystal Engineering Method; To
compare 0D [VO(TPP)] and 3D [VO(TCPP-Zn2-bpy)](3D-MOF) to investigate the influence of the spinlattice relaxation (T1) in 0D and 3D lattices. Due tothe rigid lattice of 3D-MOF, the Rabi nutation wasobserved even at room temperature (Fig.1). (2) gTensor Engineering Method; To compare [VO(TPP) and [CrN(TPP)] to investigate thecontribution of the anisotropy of their g-values for the spin relaxation. Due to the large anisotropyof g-values, [CrN(TPP)] shows the short life time. (3) Orbital Engineering Method; To compare[Ni(cyclam)X2]ClO4 and TBA[Ni(mnt)2] to investigate the relationship between the different
occupied orbitals and spin relaxation. [Ni(cyclam)X2]ClO4 has the longer life time due to the rigid
molecular structure.
As for the single molecule memory, we have used STM and STS for TbPc2 SMM. By using
tunnelling magnetoresistance, we have realized the single memory effect of up-spin and downspin on TbPc2. As for the negative magnetoresistances for high-density memory devices, we havesynthesized (BEDO-TTF)3[Co(pmdt)2] (BO3) and (BEDO-TTF)4[Co(pmdt)2] (BO4). BO3 show themetallic behavior around room temperature and M-I transition around 12K. Moreover, BO3 shows
the negative magnetoresistance for the first time by the interaction between conducting electron
and SMMs. We have succeeded the encapsulation of DySc2N@C80 SMMs into Single-Walled
Carbon Nanotubes (SWCNTs). After encapsulation, the coercivity increase by one order by
suppression of the quantum tunnelling. Finally, we have observed the negative
magnetoresistance by using Ni electrode. Moreover, we have observed Coulomb blockade effectby the interaction of conduction electron of SWCNTs and SMMs.

Coupling of structural and electronic behaviors in mixed-valence RE2.75C60
N. Yoshikane,* K. Prassides
Osaka Metropolitan University
Gakuencho 1-1, Naka-ku, Sakai, Osaka 599-8531, Japan
Email: n.yoshikane@omu.ac.jp
Buckminster fullerene C60 is one of the attractive π-electron materials to explore the novel
bulk properties come arise from electronic correlation such as high-Tc superconducting state andMott-insulator state accessible via electron injection with alkali metal doping. These behaviors are
dominated only by π-electrons reside on open-shell C60 anion, though alkali metals act as chargebalancer/spacer but not electronically active. Recent studies upon one of the families of rare-earth(RE) doped fullerides, with stoichiometry of RE 2.75C60 (RE = Sm, Yb) demonstrate the valencefluctuation of 4f electrons in RE cation sublattices are coupled to structural/electronic degree of
freedom of C60 anion sublattices. These systems are known to exhibit very similar pressure
response to that of prominent example of Kondo-insulator, samarium monosulfide[1] — pressure
driven evolution of RE oxidation states from +2 to +3 facilitates gigantic iso-symmetric latticecollapse (ΔV/V0 ~ 13%) around 6 kbar associated with optical properties changes from black to
gold.
Here we discuss our current progress in this field following the systematic mapping of thestructural and electronic behavior of the ternary (Sm 1-xCax)2.75C60 (0 ≤ x <1) fullerides[2], taking
advantage of the presence of the valence-precise divalent Ca cations. Dilution of rare-earth
concentration by calcium ion leads continuous suppression of volume collapse showing good
agreement to broadening and sluggish Sm valence evolution. Most notably, in contrast to
samarium sulfide where electron transfer associated on valence transition from Sm 2+(4f6) toSm3+(4f55d1) happens self-consistently in RE cation sublattice, the pressure-driven increase of
the Sm valence towards trivalency in (Sm1-xCax)2.75C60 leads to insulator-to-metal transitions
where excess electrons are populating the t1g-derived (LUMO+1) band (C60n−; n > 6). Thesefinding pave the new ways to access open-shell of C60 anion with tunable oxidation states upon
precise physical and chemical approaches.

Figure. (a) structural and (b) electronic pressure dependence of (Sm1-xCax)2.75C60[1] A. Jayaraman et al., Phys. Rev. Lett. 1970, 25, 1430-1433[2] N. Yoshikane et al., Mater. Chem. Front. 2020, 4, 3521-3528.

Possible role of the Tyrosine Z in the S2 to S3 transition of the Oxygen
Evolving Complex of Photosystem II
Georgia Zahariou
Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, Greece
e-mail: g.zahariou@inn.demokritos.gr
The presence of oxygen in the earth’s atmosphere is ultimately generated by the lightdriven water oxidation occurring in Photosystem II (PSII), embedded in thylakoid membranes ofplants, algae and cyanobacteria. The water evolution is catalyzed by an oxygen-bridged
Mn4CaO5 cluster, known as Oxygen Evolving Complex (OEC) of PSII. During the catalytic cycle
the OEC undergoes periodically four one-electron oxidation steps, S0-S1, S1-S2, S2-S3, S3-(S4)S0 known as S-state transitions of PSII. The O2 is released during the S3-(S4)-S0 transition, S4
being a transient [1]. The intermediates between the S-state steps involve the free radical of the
Tyrosine Z (TyrZ) and are known as metalloradical intermediate states, S iTyrZ•. Several
investigations have proven that TyrZ plays significant role in the proton coupled electron transfer
reactions, during each of the S-state steps [2-5]. TyrZ is close to the Mn4CaO5 and it functions
as an immediate electron acceptor of the cluster [2,3]. However, the involvement of TyrZ in the
proton(s) translocation process, during each S-state transition of the OEC is still unclear.
We aimed to clarify the role of TyrZ in the proton coupled electron transfer reactions
during the S2-S3 transition of the OEC in functional PSII membranes isolated from Spinacia
oleracea (spinach). For this purpose we performed a detailed EPR investigation of the S 2TyrZ•
metalloradical intermediate state, and examined the conditions under which the S 2-S3 transition
occurs. Our observations, combined with previously reported investigations [4,5] provide
important tools for the role of TyrZ in the S2-S3 transition of the OEC of PSII.
Αcknowledgements
The Max-Planck Society (Max-Planck Partner Group program, “Study of the Photosynthetic
Water splitting by Electron paramagnetic Resonance and X-ray Spectroscopy”) and NCSR
Demokritos are kindly acknowledged for the financial support.
References:
13. B. Kok, B. Forbush, M. MnGloin, Photochem. Photobiol. 11 (1970) 457
14. H. J. Eckert, G. Renger, FEBS Letters 236 (1988) 425
15. C. W. Hoganson, G. T. Babcock, Science 277 (1997) 1953
16. M. Retegan, N. Cox, W. Lubitz, F. Neese, D. A. Pantazis, Phys. Chem. Chem. Phys. 16 (2014)
11901
17. S. M. Mausle, A. Abzaliyeva, P. Greife, P. S. Simon, R. Perez, Y. Zilliges, and H. Dau, J.
Chem. Phys. 153 (2020) 215101

First Principles Calculations of Near-Resonance Raman Intensity as
Sensitive Tool for 2D Materials and Magnetic Molecules
X.-G. Zhang1,* Guanzhi Li1, Rui Zhang1, Yue Yu1, Tao Jiang2, Duy Le3, Talat S. Rahman3, HaiPing Cheng1
1

Department of Physics and the Quantum Theory Project, University of Florida, Gainesville,
Florida 32611, USA
2

Ames Laboratory, U.S. Department of Energy, Ames, Iowa 50011, USA

3

Department of Physics, University of Central Florida, Orlando, Florida 32816, USA
Email: xgz@ufl.edu

We present a fully first-principles description of the multiphonon processes in Raman scattering
under near-resonance conditions. The computational method sums over all phonon
configurations rigorously by a path-integration technique, enabling quantitative analysis ofRaman intensities near resonance, thus expanding the power of this experimental tool. The
theory is first demonstrated in an analysis of the experimental Raman spectra of MoS2/WS2
heterostructures. The relative peak intensities are correlated to stacking patterns of the bilayer,
information hitherto unavailable to conventional measurements. We also predict a multiresonance effect observable even in the single-phonon spectrum. The theory is then applied tomagnetic molecule dimers [Mn3]2. Near-resonance Raman spectra of such molecules atdifferent spin quantum state have different enhancement, making it possible to identify spinquantum state of single-molecule magnets (SMMs). By using Density Functional Theory, we
calculate optimized structures of AFM and FM configurations of [Mn3]2 in electronic ground stateand excited states, and calculate near-resonance Raman spectra in different spin quantum
states. We show that identifying features appear in the calculated resonant Raman spectra thatare absent in nonresonant Raman spectra also calculated from first-principles.
This work was supported by DOE under Award No. DE-SC0019330.

Figure. Feynman diagram representation of near-resonance Raman scattering.

Heteroaggregation Approach for depositing Spin Crossover
Nanoparticles onto Silica Coated Gold Nanorods: A Nonlinear OpticalStudy
E. Zygouri*a, V. Tangoulis a, A. Stathisb,c, S. Courisb,cDepartment of Chemistry, Laboratory of Inorganic Chemistry, University of Patras, 26504,
Patrasb
University of Patras, Department of Physics, 26504 Patras, GreececInstitute of Chemical Engineering Sciences (ICE-HT), Foundation for Research and TechnologyHellas (FORTH), P.O. Box 1414, Patras 26504.
a

Email: eleni0503zig@hotmail.com
Spin crossover (SCO) is a versatile switching phenomenon that results in remarkablechanges in magnetic, optical and mechanical properties of materials upon external perturbationsuch as light, temperature, or pressure. Molecular-based SCO compounds offer many interesting
prospects in molecular electronics. Along this line, lots of efforts have been devoted tosynthesizing and designing SCO nanoparticles (NPs) with controlled shape and size. Among SCO
materials that can be processed at the nanometer scale, while keeping the properties they exhibit
at the macroscopic scale, the attention has been driven toward polymeric triazole based iron (II)complexes. Thanks to an appropriate tuning of ligands and anions, these complexes can exhibit
a large thermal hysteresis loop between a high spin (HS) and a low spin (LS) state of iron (II)centered at room temperature. Such a hysteresis loop makes it possible to record and store
information in such compounds. The controlled synthesis of SCO nanomaterials makes it possible
to introduce many other functionalities. Coating the SCO particles with silica offers a platform tograft new functions at their surfaces, such as luminescent molecules or gold nanoparticles(AuNPs).
Hereafter we report on the coating of gold nanorods (AuNRs) by NPs of the 1D-polymericiron (II) compound with the formula [Fe(Htrz)2(trz)](BF4). For the synthesis of the SCO NPs thereverse micelle method was used leading to spheroid-like NPs covered with SiO 2 layer of 1-2 nm
and a relative size of 45 nm. AuNRs were prepared with aspect ratio AR=6.0 using the seeded
growth method while a heteroaggregation method was used for combining SCO NPs with the Au
NRs. Different concentrations of SCO NPs were prepared to study the dependence of theconcentration vs. coating of the Au NRs.
The nonlinear optical (NLO) properties of the Au NRs coated with different amounts Fe NPs
have been studied in details by means of the Z-scan technique, which allows for the simultaneous
determination of both the sign and the magnitude of the nonlinear absorption and refraction, andthe third-order nonlinear susceptibility χ(3). The measurements were performed employing the 532
and 1064 nm outputs of a 4 ns Q-switched Nd:YAG laser, in order to excite resonantly thetransverse and longitudinal Surface Plasmon Resonances (SPRs), located at ~ 530 and ~ 1060
nm, respectively.
Acknowledgment: This research has been co‐financed by the European Regional Development Fundofthe European
Union
and
Greek
national
funds
throughthe
Operational
Program Competitiveness, Entrepreneurship and Innovation, under the call RESEARCH – CREATE– INNOVATE (project code:T2EDK-01119)».

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Francesca Adami, University College Dublin, Ireland
Dimitris Alexandropoulos, University of Cyprus, Cyprus
Antonis Anastassiades, University of Cyprus, Cyprus
Alexandros S. Armenis, University of Patras, Greece
Konstantina H. Baka, University of Patras, Greece
Georgia P. Bakali, University of Patras, Greece
Vlasoula Bekiari, University of Patras, Greece
ChristiAnna Brantley, University of Florida, USA
David Britt, University of California Davis, USA
Dermot Brougham, University College Dublin, Ireland
Jaclyn Brusso, University of Ottawa, Canada
José Carvalho, Aarhus University, Denmark
Hai-Ping Cheng, University of Florida, USA
Ming-Hsi Chiang, Academia Sinica Nankang, Taiwan
Mario Chiesa, University of Torino, Italy
Sotiris Christodoulou, University of Cyprus, Cyprus
George Christou, University of Florida, USA
Maria Chrysina, INN Demokritos, NCSR Greece
Kostas Demadis, University of Crete, Creece
Selvan Demir, Michigan State Univerity, USA
Catherine Dendrinou Samara, University of Thessaloniki, Greece
Despoina Dermitzaki, INN NCSR Demokritos, Greece
Alex Diodati. University of Florida, USA
Linda Doerrer, Boston University, USA
Dimitris G. Fragkis, University of Patras, Greece
George Froudakis, University of Crete, Greece
James Fry, University of Florida USA
Miguel Gakiya-Teruya, Florida State/NHMFL, USA
Yann Garcia, IMCN/MOST Louvain, Belgium
Kleoniki Giannousi, University of Thessaloniki, Greece
Dimitris Gournis, University of Ioannina, Greece
Eleni Hadjikyprianou, University of Cyprus, Cyprus
Ashlyn Hale, University of Florida, USA
Stephen Hill, Florida State/NHMFL, USA
Stephen Holmes, University of Missouri-St. Louis, USA
Zahra Hooshmand, University of Texas at El Paso, USA
Maria Iliopoulou , University of Patras, Greece
Nikolaos Ioannidis, INN NCSR Demokritos, Greece
Andreja Jelen, Josef Stefan Institute Lubljana, Slovenia
Christopher W. M. Kay, University of Saarland, Germany

email
francesca.adami1@ucdconnect.ie
alexandropoulos.dimitrios@ucy.ac.cy

anastassiades.antonis@ucy.ac.cy
alexarmenis1996@gmail.com
mpakakonstantina645@gmail.com
Up1022666@upnet.gr
bbekiari@upatras.gr
brantley.c@ufl.edu
rdbritt@ucdavis.edu
dermot.brougham@ucd.ie
jbrusso@uottawa.ca
jose.carvalho@inano.au.dk
hping@ufl.edu
chiangmh@gate.sinica.edu.tw
mario.chiesa@unito.it
christodoulou.sotirios@ucy.ac.cy
christou@chem.ufl.edu
m.chrysina@inn.demokritos.gr
demadis@uoc.gr
sdemir@chemistry.msu.edu
samkat@chem.auth.grd.dermitzaki@inn.demokritos.gr
adiodati@chem.ufl.edu
doerrer@bu.edu
dimifrag19@gmail.com
frudakis@uoc.gr
fry@ufl.edu
mg19y@my.fsu.edu
yann.garcia@uclouvain.beklegia@chem.auth.gr
dgourni@uoi.gr
ehadji26@ucy.ac.cy
Ashlyn.rose.hale@ufl.edu
shill@magnet.fsu.edu
holmesst@umsl.edu
zhooshmand@utep.edu
marion.hliop@gmail.com
n.ioannidis@inn.demokritos.gr
andreja.jelen@ijs.si
Christopher.kay@uni-saarland.de

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Anastasios Keramidas, University of Cyprus, Cyprus
Alexandros Kitos, Ottawa University, Canda
Panayiotis Kyritsis, University of Athens, Greece
Zoi Lada, University College Dublin, Ireland
Nikolia Lalioti, University of Patras, Greece
Shengqian Ma, University of North Texas, USA

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Talal Mallah, University Paris Saclay Orsay, France
Niki Mavragani, Ottawa University, CanadMark Meisel, Universiy of Florida, USA
George Mitrikas, INN NCSR Demokritos, Greece
Grace Morgan, University College Dublin, Ireland
Muralee Murugesu, Ottawa University, Canada
Sokrates Pantelides, Vanderbilt University , USA
Konstantinos N. Pantelis, University of Patras, Greece
Ioanna Pageorgiou, University of Patras, Greece
Georgios Papavassiliou,INN NCSR Demokritos, Greece
Wassilios Papavassiliou CEA Grenoble, France
Patrina Paraskevopoulou, University of Athens, Greece
Jasper Pedersen, Technical University of Denmark, Denmark
Spyros Perlepes, University of Patras, Greece
Stergios Piligkos, University ofCopenhagen, Denmark
Michael Pissas, INN NCSR Demokritos, Greece
Kosmas Prassides, Osaka Metropolitan University, Japan
Kathryn Preuss, University of Guelph, Canada
Vassilis Psycharis, INN NCSR Demokritos, Greece
Catherine Raptopoulou, INN NCSR Demokritos, Greece
Yiannis Sanakis, INN NCSR Demokritos, Greece
Jürgen Schnack, Bielefeld University, Germany
Sotiris Skiadas, University of Patras Greece
Theocharis Stamatatos, University of Patras, Greece
Konstantinos Stamatis, INN, Demokritos, NCSR Greece
Christina Stamou, University of Patras, Greece
Aizuddin Sultan, University College Dublin, Ireland
Daniel Talham, University of Florida, USA
VassilisTangoulis, University of Patras, Greece
Anastasios Tasiopoulos, University of Cyprus, Cyprus
Nikolaos Tsoureas, University of Athens, Greece
Boris Tsukerblat, Ben-Gurion University of the Negev, Israel
Mark Turnbull, Clark University, USA
Vassilios Tzitzios, INN NCSR Demokritos, Greece
Efstathia Voudouri, University of Patras, Greece
Ziling (Ben) Xue, University of Tennessee, USA

akeramid@ucy.ac.cy
akitos@uottawa.ca
kyritsis@chem.uoa.gr
zoi.lada@ucd.ie
lali@upatras.gr
Shengqian.Ma@unt.edu
talal.mallah@universite-parissaclay.fr
nmavr078@uottawa.ca
meisel@phys.ufl.edu
g.mitrikas@inn.demokritos.gr
grace.morgan@ucd.ie
m.murugesu@uottawa.ca
pantelides@vanderbilt.edu
kostaspantelis95@gmail.com
up1073657@upnet.gr
g.papavassiliou@inn.demokritos.gr
wassilios.papawassiliou@cea.fr
paraskevopoulou@chem.uoa.gr
kastp@kemi.dtu.dk
perlepes@upatras.gr
piligkos@chem.ku.dk
m.pissas@inn.demokritos.gr
k.prassides@omu.ac.jp
kpreuss@uoguelph.ca
v.psycharis@inn.demokritos.gr
c.raptopoulou@inn.demokritos.gr
i.sanakis@inn.demokritos.gr
jschnack@uni-bielefeld.de

up1055861@upnet.gr
thstama@upatras.gr
konstamat21@gmail.com
xrstamou@gmail.com
Aizuddin.sultan@ucdconnect.ie
talham@chem.ufl.edu
vtango@upatras.gr
tasiopoulos.anastasios@ucy.ac.cy
ntsoureas@chem.uoa.gr
tsuker@bgu.ac.il
mturnbull@clarku.edu
v.tzitzios@inn.demokritos.gr
efi.voudouri@gmail.com
xue@utk.edu

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Masahiro Yamashita, Tohoku University, Japan
Naoya Yoshikane, Osaka Metropolitan University, Japan
Georgia Zahariou, INN Demokritos, NCSR Greece
Xiaoguang Zhang, University of Central Florida, USA
Eleni Zygouri, University of Patras, Greece

yamasita.m@gmail.com
n.yoshikane@omu.ac.jp
g.zahariou@inn.demokritos.gr

xgz@ufl.edu
eleni0503zig@hotmail.com