bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Nanostructuration and Application of Supramolecular Materials through 1D, 2D and 3D-Hydrogen Bond-Directed Self-Assembly
Authors: Curiel David , Gómez Paula , Giménez Isaac , Carrera Manuel , Más-Montoya Miriam , Georgakopoulos Stamatis , Mora-Seró Iván , Méndez Javier 
Published: September 2023

Self-assembly is a useful tool in Chemistry for the development of organized supramolecular systems stabilized by non-covalent interactions.[1] The rational design of organic molecules that suitably integrate different interacting sites into their structure becomes an attractive approach to control the molecular arrangement by exploiting the driving force of those non-covalent interactions.[2] With this objective in mind, we have synthesized a series of π-conjugated molecules that incorporate the 7-azaindole unit as building block to induce the supramolecular self-assembly in the solid state through reciprocal hydrogen bonding.[3]

The judicious alteration of the molecular geometry has demonstrated the adequacy of this self-assembly strategy to achieve the control on the directionality of N-H···N hydrogen bond interactions. Consequently, 1D, 2D and 3D-supramolecular systems have been obtained with interesting structural properties.[4] In this communication we present our recent advances in this approach towards supramolecular materials, particularly focusing on their application as organic semiconductors in devices such as Organic Field Effect Transistors and perovskite solar cells.[5] The performance of these novel molecules as hole transporting materials has revealed a remarkable robustness despite their non-covalent nature. Accordingly, these results offer a proof of concept about the potential utility of supramolecular self-assembly in the development of novel nanostructured materials.

References

[1] S. I. Stupp, L. C. Palmer, Chem. Mater.
2014, 26, 507-518.
[2] a) K. S. Mali, N. Pearce, S. De Feyter, N. R. Champness, Chem. Soc. Rev.
2017, 46, 2520-2542; b) R.-B. Lin, Y. He, P. Li, H. Wang, W. Zhou, B. Chen, Chem. Soc.
Rev.
2019, 48, 1362-1389.
[3] P. Gómez, J. Cerdá, M. Más-Montoya, S. Georgakopoulos, I. da Silva, A. García, E. Ortí, J. Aragó, D. Curiel, J. Mater. Chem. C
2021, 9, 10819-10829.
[4] L. M. Rodríguez, P. Gómez, M. Más-Montoya, J. Abad, A. Tárraga, J. I. Cerdá, J. Méndez, D. Curiel, Angew. Chem. Int. Ed.
2021, 60, 1782-1788.
[5] a) P. Gómez, J. Wang, M. Más-Montoya, D. Bautista, C. H. L. Weijtens, D. Curiel, R. A. J. Janssen, Solar RRL
2021, 5, 2100454; b) P. Gómez, S. Georgakopoulos, M. Más-Montoya, J. Cerdá, J. Pérez, E. Ortí, J. Aragó, D. Curiel, ACS Appl.
Mater. Interfaces
2021, 13, 8620-8630.

Acknowledgements

Ministry of Science, Innovation and Universities (Project RTI2018-101092-B-I00). Fundación Séneca - Agencia de Ciencia y Tecnología de la Región de Murcia (Project 20959/PI/18). Programa Estatal de Fomento de la Investigación Científica y Técnica de Excelencia (RED2018-102815-T).

Figure 1
(Invited) Smart Molecular/2D Heterostructures
Authors: Coronado Eugenio 
Published: September 2023

Graphene and other 2D materials are almost exclusively based on inorganic lattices. Except for the chemical functionalization of the surface of the 2D material, molecules have been scarcely considered in this area. Here I propose to create hybrid heterostructures by interfacing stimuli-responsive molecular systems with graphene and semiconducting transition metal dichalcogenides (MoS2 and WSe2). The aim is that of tuning the properties of the “all surface” 2D material via an active control of the hybrid interface. This concept will provide an entire new class of smart molecular/2D heterostructures, which may be at the origin of a novel generation of hybrid materials and devices of direct application in highly topical fields like electronics, spintronics and energy storage. As smart-molecular systems I will choose magnetic spin-crossover materials able to switch between two spin states upon the application of an external stimulus (temperature, light or pressure) [2]. This spin transition is always accompanied by a significant change of volume in the material (by ca. 10%), so it can generate strain in its surroundings. I will show that in these heterostructures the electronic properties of graphene and the optical photoluminescence of monolayers of semiconducting metal dichalcogenides can be switched by light or by varying the temperature due to the strain concomitant to the spin transition [3, 4].

References

[1] J. Lopez-Cabrelles et al., J. Am. Chem. Soc. 143 18502-18510 (2021).
[2] E. Coronado, Nature Rev. Mater. 5 87-104 (2020).
[3] R. Torres-Cavanillas et al. Nature Chem. 13 1101-1109 (2021).
[4] C. Boix-Constant et al. Adv. Mater. 34 2110027 (2022).
(Invited) Modification of Properties of N- and B-Doped Graphene by Heteroatom Functionalization
Authors: Arellano Luis M , Barrejon Myriam , Gómez-Escalonilla Romojaro Maria , Langa Fernando 
Published: September 2023

Since its discovery in 2004, the graphene has attracted great attention owing to its unique chemical bonding structure, which has excellent chemical, thermal, mechanical, electrical and optical properties. Due to the graphene being a zero band-gap material, it has a limited development in the field of nano electronics. Therefore, to broaden its application scope, it is very important to carry out a study on opening the band gap of graphene. One general strategy for achieving this goal is doping graphene with heteroatoms; in this approach, the properties of graphene are controlled by the nature of the dopant elements and by the percentage of doping being N-doped graphene is of n-type doping, while B-doped graphene is of p-type doping. Compared with that of the intrinsic graphene, the Fermi level of N doped graphene moves up 5 eV; on the contrary, the Fermi level of B doped graphene moves down 3 eV.
However, it would be convenient to develop additional tools to achieve further control of the electronic properties of graphene materials. In this context, one of the possibilities would be to functionalize those dopant elements on the graphene sheet in such a way that the electron density and electronegativity of the heteroatom are effectively controlled. This objective could, in principle, be achieved by applying concepts from organic chemistry. Organic synthesis offers proven chemical reactions that are applicable to different types of nitrogen and boron compounds.
In the work described here, we´ll present our results on the covalent functionalization of the nitrogen atom or boron atom of N-doped and B-doped graphene. In a simple strategy, electron-donating and -withdrawing groups present on aromatic rings can be used to modulate the electronic properties of the material.
References
[1] M. Barrejón, A. Primo, M. J. Gómez-Escalonilla, J. L. García-Fierro, H. García, F. Langa, Chem. Comm. 2015, 51, 16916-16919.
[2] M. Barrejón, L. M. Arellano, H. B. Gobeze, M. J. Gómez-Escalonilla, J. L. García-Fierro, F. D’Souza, F. Langa, Chem. Sci. 2018, 9, 8221–8227.
[3] H. B. Gobeze, L. M. Arellano, A. M. Gutiérrez-Vílchez, M. J. Gómez-Escalonilla, Á. Sastre-Santos, F. Fernández-Lázaro, F. Langa, F. D’Souza, Nanoscale Adv, 2019, 1, 4009-4015.
[4] L. M. Arellano, S. Yue, P. Atienzar, M.J. Gómez-Escalonilla, F.J. Ortega-Higueruelo, J.L.G. Fierro,H. García, F. Langa. Chem. Commun., 2019, 55, 9999.
[5] L. M. Arellano, H. B. Gobeze, Y. Jang, M. Barrejón, C. Parejo, J. C. Álvarez, M. J. Gómez-Escalonilla, A. Sastre-Santos, F. D’Souza, F. Langa, Chem. Eur. J, 2022 (https://doi.org/10.1002/chem.202200254)
(Invited) Making Stacks of Nitrogenated Polycyclic Aromatic Hydrocarbons with Hydrogen Bonds
Authors: Mateo-Alonso Aurelio 
Published: September 2023

Architectures constituted of stacked aromatics play a crucial role in the development of function in biomacromolecules. Recreating this feature on synthetic systems would not only allow understanding and reproducing biological functions but also developing new functions. For instance, the performance of organic field-effect transistors, light-emitting diodes, and solar cells critically depends on the charge transport efficiency of stacks of organic semiconductors. Among different packing configurations, lamellar π-stacking has been identified as an optimal configuration for electronic transport, because of the efficient intermolecular electronic coupling.
Nitrogenated polycyclic aromatic hydrocarbons and nanographenes have attracted considerable attention in recent years. Besides the effect of nitrogen doping on the electronic structure, sp2 nitrogens can be engaged in hydrogen bonding interactions as acceptors. We have developed the synthesis of novel architectures constituted of stacked nitrogenated polycyclic aromatic hydrocarbons held together by hydrogen bonds, which include new families of pseudorotaxanes, rotaxanes, foldamers and supramolecular polymers. The synthesis and self-assembling properties of these systems will be discussed together with their charge transporting properties.

References

[1] A. Riaño, M. Carini, M. Melle-Franco and A. Mateo-Alonso, J. Am. Chem. Soc.
2020, 142, 48, 20481-20488.
[2] M. Carini, M. Marongiu, K. Strutyński, A. Saeki, M. Melle-Franco, and A. Mateo-Alonso, Angew. Chem. Int. Ed.
2019, 58, 15788-15792.
[3] C. Gozalvez, J. L. Zafra, A. Saeki, M. Melle-Franco, J. Casado and A. Mateo-Alonso, Chem. Sci., 2019, 10, 2743-2749.
[4] M. Carini, M. P. Ruiz, I. Usabiaga, J. A. Fernández, E. Cocinero, M. Melle-Franco, I. Diez-Perez, and A. Mateo-Alonso, Nat.
Commun., 2017, 8, 15195.

Figure 1
(Invited) Conjugated Metallophthalocyanine as Hole-Transporting Materials for Improved Stability in Perovskite Solar Cells
Authors: Sastre-Santos Ángela 
Published: September 2023

Perovskite solar cells (PSCs) are promising candidates to reach the market to complement the current offer of photovoltaic cells although for such a thing they still have to overcome some challenges such as long-term stability. The hole transporting layer (HTL) is a crucial component in n-i-p PSC, since it must favor an adequate movement of charges and protect the perovskite layer from environmental conditions. In this sense, the commonly used HTL, spiro-OMeTAD, does not provide PSCs with sufficient stability and is too expensive. Cheaper molecular materials such as metallophthalocyanines are proving to be a good alternative, as they provide greater stability.[1]
In this communication, we will present the synthesis of novel ZnPcs and CuPcsmonomers [2] and ZnPc dimers [3] (see as examples Figure 1) as efficient, stable, and low cost HTMs in PSCs. The MPcs are substituted with functional groups that possesses a very good solubility in a wide range of organic solvents, adequate HOMO LUMO levels and thus can be applied from solution processing in a wide range of perovskite solar cell devices.

References

1. M. Urbani, M. E. Ragoussi, M. K. Nazeeruddin, T. Torres, Coord. Chem. Rev.
2019, 381, 1-64.
2. P. Huang, A. Hernández, J. Follana-Berná, S. Kazim, J. Ortíz, Á. Sastre-Santos, S. Ahmad, ACS Appl. Energy Mater.
2021, 4, 9, 10124–1013
3. D. Molina, M. Pegu, M. João Álvaro-Martins, L. Ferrer, M. Castillo, S. Kazim, S. Ahmad, Á. Sastre-Santos, J. Mater. Chem. C, 2022, 10, 11975-11982.

Figure 1
(Invited) Interplay Between π–Conjugation and Exchange Magnetism in One-Dimensional Porphyrinoid Polymers
Authors: Biswas Kalyan , Urbani Maxence , Sánchez-Grande Ana , Soler Diego , Lauwaet Koen , Miranda Rodolfo , Ecija David , Torres Tomas , Jelínek Pavel , Urgel Jose 
Published: September 2023

The field of carbon magnetism has gained an increased attention in view of the recent progress made in the synthesis and characterization of open-shell polycyclic aromatic hydrocarbons following a bottom-up synthetic approach[1,2]. Under this scenario, the comprehensive fabrication of magnetic porphyrinoid-based polymers emerges as a highly appealing field of research. However, the vast majority of the porphyrinoid species and polymers studied to date exhibit a closed-shell ground state[3].
In this work, we introduce an exemplary approach toward the bottom-up fabrication of unprecedented magnetic porphyrinoid-based polymers homocoupled via surface-catalyzed [3 + 3] cycloaromatization of isopropyl substituents studied on Au(111) under ultra-high vacuum (UHV) conditions. The chemical structure of the polymer, formed by thermal-activated intra- and intermolecular oxidative ring closure reactions followed by controlled tip-induced hydrogen dissociation from the porphyrinoid units, have been clearly elucidated by scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). Scanning tunneling spectroscopy (STS), complemented by computational investigations reveals the open-shell character, i.e. antiferromagnetic singlet ground state (S=0) of the formed polymers, which display singlet−triplet inelastic excitations observed between spins of adjacent porphyrinoid units only along a specific π-conjugation pathway, thus revealing the interplay between π-conjugation and magnetic exchange. We envision that our approach can be a highly relevant step towards the on-surface synthesis of covalently linked 1D magnetic organic polymers with prospects in nanoscale spintronic devices.
References:
[1] Auwärter, W.; Écija, D.; Klappenberger, F.; Barth, J. V. Porphyrins at Interfaces. Nat Chem. 2015, 7 (2), 105–120.
[2] Gottfried, J. M. Surface Chemistry of Porphyrins and Phthalocyanines. Surf. Sci. Rep. 2015, 70 (3), 259–379.
[3] Shimizu, D.; Osuka, A. Porphyrinoids as a Platform of Stable Radicals. Chem. Sci. 2018, 9 (6), 1408–1423.
Figure caption: On-surface reaction scheme toward the synthesis of one-dimensional porphyrinoid polymers starting from precursor 1 to magnetic porphyrinoid polymer 3 with intermediate non-magnetic porphyrinoid-based polymer 2

Figure 1
(Nanocarbons Division Robert C. Haddon Research Award) Nano Carbons in Mimicking the Early Events of Photosynthetic Reaction Center: ‘Simple’ and ‘Not-so-Simple’ Donor-Acceptor Conjugates
Authors: D'Souza Francis 
Published: September 2023

Light-induced electron transfer is a key step in solar energy conversion, and a process with myriad relevance in the fields of artificial photosynthesis, photocatalysis, photoconductivity, and photovoltaics. In a donor-acceptor, D-A system, light absorption by a chromophore results in the formation of an excited state species, followed by a charge transfer between an electron donor (D) and an electron acceptor (A) leading to a charge-separated D
.+
-A
.-
species.The optimization of these processes and comprehending their mutual interplay to ultimately achieve charge-separated species is of paramount importance for the development of efficient systems in solar light conversion schemes.
The present talk summarizes our research over the years focused on utilizing nano carbons, viz., fullerenes, endohedral fullerenes, carbon nanotubes, and graphene in the construction of donor-acceptor systems capable of undergoing photoinduced energy and electron transfer events. Both, covalently linked with rigid, semi-rigid, flexible, or conjugated spacers, and self-assembled via metal-ligand axial coordination, ion-pairing, ion-dipole, or hydrogen bonding strategies were utilized in the construction of donor-acceptor conjugates. Multi-modular donor-acceptor constructs were designed, synthesized, and studied to probe sequential energy and electron transfer events, finally resulting in long-lived charge-separated states. In some instances, these molecular systems were also used as photocatalytic energy conversion schemes. The pros and cons of utilizing nanocarbon materials as photo-active functional materials will be highlighted.

D’Souza, F.; Sandanayaka, A. S. D.; Ito, O. ‘SWNT-Based Supramolecular Nanoarchitectures with Photosensitizing Donor and Acceptor Molecules’ Phys. Chem. Letts. 2010, 1. 2586-2593.

D’Souza, and O. Ito ‘Photosensitized electron transfer processes of nano carbons applicable to solar cells,’ Chem. Soc. Rev. 2012,
41, 86-96.

B. KC, F. D’Souza, ‘Design and photochemical study of supramolecular donor-acceptor systems assembled via metal-ligand axial coordination Coord. Chem. Rev. 2016, 322, 104-141.

Bottari, M. A. Herranz, L. Wibmer, M. Vollard, L. Rodriguez-Perez, D. M. Guldi, A. Hirsch, N. Martin, F. D’Souza, T. Torres, Chemical functionalization and characterization of graphene-based materials, Chem. Soc. Rev. 2017, 46, 4464-4500.

Barrejon, L. M. Arellano, F. D’Souza, F. Langa, ‘Bidirectional charge transfer in carbon-based hybrid nanomaterials’ Nanoscale, 2019, 11, 14978-14992.

Kazemi, Y. Jang, A. Liyanage, P. A. Karr, and F. D’Souza, ‘A Carbon Nanotube Binding Bis(pyrenylstyryl)BODIPY-C60 Nano Tweezer: Charge Stabilization through Sequential Electron Transfer’, Angew. Chem. Int. Ed.
2022, in press
(Invited) Water-Based and Defect-Free 2D Material Inks for Printed Electronics
Authors: Casiraghi Cinzia 
Published: September 2023

2D materials show great promise for use in flexible electronics because their atomic thickness allows for maximum electrostatic control, optical transparency, sensitivity and mechanical flexibility. In addition, different 2D crystals can be easily combined in one stack, offering unprecedented control on the performance and functionalities of the resulting heterostructure-based device. In addition, solution processing of 2D materials allows simple and low-cost techniques, such as ink-jet printing, to be used for fabrication of heterostructure-based devices of arbitrary complexity.
Our group has developed highly concentrated, defect-free, biocompatible, inkjet printable and water-based 2D crystal formulations, by exploiting a supramolecular approach based on non-covalent functionalization of 2D materials with pyrene derivatives [1]. Examples of printed heterostructures, such as arrays of photosensors, programmable logic memories, transistors and memristors will be discussed [2-3]. I will show that inkjet printing can be easily combined with semiconducting 2D materials produced by chemical vapor deposition, allowing simple and quick fabrication of complex circuits on paper, compatible with CMOS technology [4-5] and also offers a simple way to integrate 2D materials into Si-based technology [6].
References:
[1] Chen-Xia Hu, Yuyoung Shin, Oliver Read, Cinzia Casiraghi, Dispersant-assisted liquid-phase exfoliation of 2D materials beyond graphene, Nanoscale, 2021, 13, 460
[2] McManus, D., Vranic, S., Withers, F. et al. Water-based and biocompatible 2D crystal inks for all-inkjet-printed heterostructures. Nature Nanotech 12, 343–350 (2017)
[3] Shiheng Lu Shiheng Lu Department of Electrical and Computer Engineering, Duke University, Durham, North Carolina 27708, United States More by Shiheng Lu Orcidhttp://orcid.org/0000-0002-5323-7787 , Jorge A. Cardenas, Robyn Worsley, Nicholas X. Williams, Joseph B. Andrews, Cinzia Casiraghi, and Aaron D. Franklin, Flexible, Print-in-Place 1D–2D Thin-Film Transistors Using Aerosol Jet Printing, ACS Nano 2019, 13, 10, 11263–11272
[4] Silvia Conti, Lorenzo Pimpolari, Gabriele Calabrese, Robyn Worsley, Subimal Majee, Dmitry K Polyushkin, Matthias Paur, Simona Pace, Dong Hoon Keum, Filippo Fabbri, Giuseppe Iannaccone, Massimo Macucci, Camilla Coletti, Thomas Mueller, Cinzia Casiraghi, Gianluca Fiori, Low-voltage 2D materials-based printed field-effect transistors for integrated digital and analog electronics on paper. Nat Commun 11, 3566 (2020)
[5] Brunetti, I., Pimpolari, L., Conti, S. et al. Inkjet-printed low-dimensional materials-based complementary electronic circuits on paper. npj 2D Mater Appl 5, 85 (2021).
[6] Alessandro Grillo, Zixing Peng, Aniello Pelella, Antonio Di Bartolomeo, Cinzia Casiraghi, Etch and Print: Graphene-Based Diodes for Silicon Technology, in press
Real-Time Detection and Speciation of Mn Dissolution in a Li-Ion Battery Cathode
Authors: Zhao Dongni , Mertens Stijn F. L. 
Published: September 2023

Rechargeable lithium-ion batteries (LIB) are widely used in portable electronic devices, electric vehicles, medical devices, etc. thanks to their improved performance in recent decades. The properties of the cathode still largely limit the overall performance, as the cathode usually has lower theoretical capacity and suffers from more serious degradation effects.1 Among these, dissolution of transition metals is an important but poorly understood side reaction. On the one hand, it dominates the cathode capacity fading by causing irreversible loss of active redox sites, phase transformation, cation mixing, grain fracture, etc. On the other hand, the dissolved transition metal ions can exacerbate the formation of the solid electrolyte interphase (SEI) on the anode through a dissolution-migration-deposition (DMD) process.2

Here, we focus on the dissolution of manganese from LiMn2O4 (LMO), a benchmark cathode material, through real-time analysis of the electrolyte by combining online inductively coupled plasma–optical emission spectroscopy (online ICP-OES) and rotating ring-disc electrode (RRDE) collection, Figure 1. Both methods offer real-time dissolution information as functions of time and potential/state of charge, while the former shows superior detection limits and the latter provides oxidation state information of the dissolving species.
According to online ICP-OES, we find that Mn dissolves readily from fully lithiated LMO when brought in contact with aqueous 0.2 M Li2SO4, but that a dissolution-passivation process stops further detectable dissolution until well past fully delithiated λ-MnO2. The dissolution becomes detectable again on the returning scan to the potential of pristine LMO, and grows exponentially in the overlithiated region.3 Our RRDE results indicate that Mn2+ is the dominating dissolved Mn species only in overlithiation region, whereas it only accounts for a minor proportion in the dissolved species from delithiation region. The data from both techniques suggest that the dissolution of Mn is related to the surface state of the electrode, rather than its degree of lithiation, as widely believed in the past.4

Our results provide a better understanding of the mechanism of transition metal dissolution in cathode materials, as well as an entry point for screening next-generation cathodes and metal ion batteries with superior degradation characteristics.5

References:

C. Zhan, T. Wu, J. Lu and K. Amine, Energy Environ. Sci., 2018, 11, 243–257.

Y. K. Lee, J. Park and W. Lu, J. Electrochem. Soc., 2017, 164, A2812–A2822.

S. Nikman, D. Zhao, V. Gonzalez-Perez, H. E. Hoster and S. F. L. Mertens, Electrochim. Acta, 2021, 386, 138373.

J. C. Hunter, J. Solid State Chem., 1981, 39, 142–147.

N. Tapia-Ruiz, S. F. L. Mertens et al., J. Phys.: Energy, 2021, 3, 031503.

Figure 1