bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Preparation and Characterization of WS2–TiO2–Au Nanohybrid System Using Hydrothermal Synthesis for Photocatalysis Under Visible Light
Authors: Furube Akihiro , Wu Kejun , Pankaj Koinkar 
Published: July 2022

We have developed a new visible light responsive photocatalytic material by combining tungsten disulfide (WS2), a nanosheet semiconductor material that has attracted much attention in recent years, gold nanoparticles that strongly absorb visible light, and titanium dioxide (TiO2), a highly active photocatalyst1. Ultrasonic milling and hydrothermal synthesis methods were utilized to successfully synthesize the ternary nanohybrid materials and improve their visible light photocatalytic performance. The mechanism was elucidated based on the detailed characterization of structural properties, spectroscopic properties, photocatalytic reaction properties, and electron transfer reaction dynamics using femtosecond transient absorption spectroscopy.
Reference

Kejun Wu, Pankaj Koinkar, and Akihiro Furube, International Journal of Modern Physics B, 35, 2140046 (2021)
(Digital Presentation) Photopolymerization of Tetraazaporphyrin Based Surfactants and Mesogens
Authors: Eichhorn S. Holger , Rondeau-Gagné Simon , Abdulhamied Elmahdy , Tahir M Nazir 
Published: July 2022

Intermolecular interactions between tetraazaporphyrin (TAP) macrocycles are less dominated by π-π stacking interactions than interactions between their larger phthalocyanine derivatives. Consequently, the self-organization and -assembly of TAPs is more widely altered by changes to the type of complexed metal ion and substitution pattern. Presented here are different molecular designs for mesomorphic and amphiphilic TAPs that could be cross-linked by “click” chemistry and by the photo and thermal polymerization of diacetylene groups. All compounds were studied by polarized optical microscopy, thermal analysis, and X-ray diffraction to probe their (meso)phase structures and transitions and by the Langmuir-Blodget method to quantify their interfacial properties. Potential applications for these compounds include their use as active materials in sensors, functional coatings for metal oxide nanoparticles, and building blocks for dye nanoparticles.
Topochemical Polymerization of a Nematic Tetraazaporphyrin Derivative to Generate Soluble Polydiacetylene Nanowires. M. Nazir Tahir, et al., 2019, Langmuir, 35(47) 15158−15167.
Self-organization of Porphyrins and Phthalocyanines in two and three dimensions by S. Holger Eichhorn and Elmahdy Abdulhamied, in “Handbook of Porphyrin Science: Towards Tuned Properties of Porphyrinoids”, Vol. 42, Karl M. Kadish, Kevin M. Smith, Roger Guilard, Eds., World Scientific, Singapore, 2016, 173-232.
Cross-linking of discotic tetraazaporphyrin dyes in 2 and 3 dimensions by “click” chemistry. Himadri Kayal, et al., 2013, J. Mater. Chem. C, 1(42), 7064-7072.
Face- and edge-on orientations of octa-acid and -alcohol substituted tetraazaporphyrins in langmuir and Langmuir-Blodgett monolayers. M. M. Ahmida, et al., 2013, Soft Matter 9 (3), 811-9.
Triarylcorrole Vs Octaalkylcorrole: Similar but Different
Authors: Paolesse Roberto , Nardis Saar , Naitana Mario L. , Di Zazzo Lorena 
Published: July 2022

The chemistry of corroles is still an open field of investigation able to deliver new and unexpected results especially when they a peculiar reactivity, different from the parent porphyrins.
The genesis of corrole is derived from the Johnson attempt to elaborate a synthetic route for the preparation vitamin B12 and the corrole name is due to the molecular skeleton of this macrocycle, similar to that of the corrin nucleus. The interest on this macrocycle has been boosted by the definition of synthetic routes for the preparation of 5,10,15-triarylcorroles, which make facile to prepare and consequently investigated the chemistry of this macrocycle. As a consequence, the chemistry of b-octaalkylcorroles has been shadowed by the expansion of the triaryl congeners.
However, the chemistry of these two types of corrole show some interesting differences and in this contribution we want to show some examples of this different behavior.
Use of Porphyrin Containing Porous Materials in Heterogeneous Catalyst
Authors: Lee Suk Joong , Yoon Jong Ho 
Published: July 2022

Due to their potential applications in catalysis, separation, gas storage, drug delivery, and biosensing, porous materials (PMs) such as porous organic polymers (POPs), polymers with intrinsic microporosity (PIMs), porous coordination polymers (PCPs), and metal–organic frameworks (MOFs), have received much attention. Various building blocks have been prepared and demonstrated various functional materials. Among the various organic building blocks, porphyrin has become one of the most important building blocks for the construction of such materials witnessed by a wide range of molecular architectures using porphyrin derivatives with various applications. Mn(III)- and Fe(III)-containing metalloporphyrins are often used to fabricate various functional molecular architectures and to mimic the extraordinary behavior of enzymes in both homogeneous and heterogeneous catalytic systems. In the case of homogeneous catalysis, Mn(III)- and Fe(III)-containing metalloporphyrins have frequent trouble with fast catalytic degradation because of µ-oxo dimer formation or ligand oxidation. To avoid the catalyst degradation, the immobilization and/or site-isolation of homogeneous catalysts using supporters such as polymers, membranes, and MOFs, are widely used strategy. In addition, they are often used to modify the surface of porous silica materials such as SBA-15, MCM-41 and MCM-48, because these porous silica materials exhibit narrow pore size distributions, high thermal stability and easy accessibility.
In this presentation, we like to show the use of metalloporphyrins in various porous materials and their use as heterogeneous catalysts.
References

D. Y. Shin, J. H. Yoon, S. H. Kim, H. Baik, S. J. Lee,* "Immobilization of Porphyrinic Mn(III) Catalyst on a New Class of Silica Support Comprising Three-Dimensionally Interconnected Network with Two Different Sizes of Pores",
Catal. Sci. Technol. 2018, 8, 6306-6310.

J. Yi, H. Y. Jeong, D. Y. Shin, C. Kim, S. J. Lee,* "Mn(III)-Porphyrin Containing Heterogeneous Catalyst based on Microporous Polymeric Constituents as a New Class of Catalyst Support",
ChemCatChem 2018, 10, 3974-3977.

J. Yoon, H. M. Choi, S. J. Lee,* "Cu(II)Cl2 containing bispyridine-based porous organic polymer support prepared via alkyne–azide cycloaddition as a heterogeneous catalyst for oxidation of various olefins",
New J. Chem. 2020, 44, 9149-9152.

H. M. Choi, Y. J. Kim, E. T. Choi, S. J. Lee,*
"Selective Photocatalytic Oxidative Detoxification of a Chemical Warfare Agent Simulant by Porphyrin-Containing Polymers of Intrinsic Microporocity."
ACS Appl. Polym. Mater.2021,
submitted
.
Synthesis and Electrochemical Investigation of π Expanded Vitamin B12 Derivative, Pyrocobester
Authors: Shichijo Keita , Hisaeda Yoshio , Shimakoshi Hisashi 
Published: July 2022

Vitamin B12 is a unique metal complex which has the cobalt ion and the corrin as a centered metal and a ligand, respectively. The Co(I) state of the vitamin B12 reacts alkyl halide to form alkylated complex by the SN2 type reaction and proceed the several catalytic reactions via alkyl radicals formed by homolysis of the cobalt-carbon bond.[1] Based on these properties of the vitamin B12, many B12-inspired reactions have been developed.[2] In general, many researchers have used the cobyrinate complex (1) as the B12 derivatives. Here, we report the synthesis and characterization of the Co(II) state of pyrocobseter (2) with π-expanded structure and the reactivities of the complex will be discussed.
The pyrocobester was synthesized by the pyrolysis of the cobyrinate.[3] The absorption of the pyrocobester showed efficiently red-shift compared to the cobyrinate because of the conjugated corrin ligand. Furthermore, Co(II)/Co(I) redox potentials were +0.3 V shifted (Figure 1). In addition, the spectrum was dramatically changed after adding the CH3I as the substrate. It is suggested that Co(I) state of pyrocobester reacted with CH3I and alkylated complex (CH3-Co(III)) was formed. In this presentation, we will report experimental detail of pyrocobester chemistry.
References
[1] D. Gryko et al., Chem. Soc. Rev., 2015, 44, 3391.
[2] H. Shimakoshi, Y. Hisaeda, Chem. Rec., 2021, 21, 2080.
[3] B. Kraütler et al., Helv. Chim. Acta., 1983, 66, 1493.

Figure 1
On-Surface Synthesis of Fused Anthracenyl Porphyrin Derivatives
Authors: Pijeat Joffrey , Baljozovic Milos , Lamare Raphael , Ernst Karl-Heinz , Campidelli Stephane 
Published: July 2022

For the last fifteen years, on-surface synthesis became an extremely popular and powerful method to fabricate nanostructures which otherwise would not have been accessible by conventional wet organic syntheses. The syntheses, realized in the chamber of high vacuum scanning tunneling microscope (STM), permitted the fabrication and the characterization of atomically defined nanostructures such as polycyclic aromatic hydrocarbons (PAH), graphene nanoribbons or 2D covalent networks.1 Among the organic molecules studied by STM, porphyrins are of particular importance because of their electronic and optical properties. Initial studies were mainly devoted to the supramolecular organization of porphyrins and porphyrin derivatives on surface and it is only in 2004 that noble metal surfaces were used as catalytic surface to perform reactions on the porphyrin cores.2 Since then, examples of open-shell porphyrin derivatives3 and conjugated oligomers4 were reported.
While the synthesis of fused bis- and tetra-4,5-bis-(2,4,6-trimethylphenoxy)anthracen-9-yl porphyrins containing Ni(II) was reported by Anderson about 10 years ago,5 the formation π-extended porphyrin bearing unsubstituted anthracenyl moieties were never achieved. The formation of such compounds became possible by on-surface synthesis. Herein, we report on the synthesis of fused bis- and tetra-anthracenylporphyrin derivatives via the cyclodehydrogenation the parent meso-substituted molecules on a catalytic Au(111) surface.6 Depending on the annealing temperature, anthracenylporphyrins with the four anthracene fully linked to the porphyrin core or over-oxidized porphyrin in which the anthracene are connected two by two in 2-2’ position were observed by STM (Figure 1).

Figure 1. STM images of the fused tetra-anthracenylporphyrins and related porphyrin structures

References

Clair, S.; de Oteyza, D. G. Chem. Rev.
2019, 119, 4717-4776.

Fox, S.; Boyle, R. W. Chem. Commun.
2004, 1322-1323.

a) Sun, Q.; Mateo, L. M.; Robles, R.; Ruffieux, P.; Lorente, N.; Bottari, G.; Torres, T.; Fasel, R. J. Am. Chem. Soc.
2020, 142, 18109-18117; b) Zhao, Y.; Jiang, K.; Li, C.; Liu, Y.; Xu, C.; Zheng, W.; Guan, D.; Li, Y.; Zheng, H.; Liu, C.; Luo, W.; Jia, J.; Zhuang, X.; Wang, S. J. Am. Chem. Soc.
2020, 142, 18532-18540.

a) Mateo, L. M.; Sun, Q.; Liu, S.-X.; Bergkamp, J. J.; Eimre, K.; Pignedoli, C. A.; Ruffieux, P.; Decurtins, S.; Bottari, G.; Fasel, R.; Torres, T. Angew. Chem., Int. Ed.
2020, 59, 1334-1339; b) Mateo, L. M.; Sun, Q.; Eimre, K.; Pignedoli, C. A.; Torres, T.; Fasel, R.; Bottari, G. Chem. Sci.
2021, 12, 247-252.

a) Davis, N. K. S.; Thompson, A. L.; Anderson, H. L. Org. Lett.
2010, 12, 2124-2127; b) Davis, N. K. S.; Thompson, A. L.; Anderson, H. L. J. Am. Chem. Soc.
2011, 133, 30-31.

Baljozović, M. et al., in preparation

Figure 1
Recent Advances in Zinc Anc Cooper Phthalocyanines As Hole Transporting Materials in Perovskite Solar Cells
Authors: Sastre-Santos Angela 
Published: July 2022

Recently, significant progresses have been achieved in the fabrication of highly efficient perovskite solar cells, while major challenges, such as commercial viablity of exotic materials and their instability, remain as an obstacle. Hole transporting materials (HTMs) represent a tricky choice for the fabrication of efficient solar cells and the cost uneffective Spiro-OMeTAD continue to be so far the most obvious candidate. Semiconductors molecules, such as metallophthalocyanines (MPcs)1 appeared as a promising class of p-type material, since they are less expensive and more stable.
In this communication, we will present the synthesis of novel ZnPcs,2 ZnPc dimers3 and CuPcs4 (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.
Figure 1. Different ZnPcs structures as HTMs in PSCs

References

M. Urbani, M. E. Ragoussi, M. K. Nazeeruddin, T. Torres, Coord. Chem. Rev.
2019, 381, 1-64.

P. Huang, A. Hernández, S. Kazim, J. Ortíz, Á. Sastre-Santos, S. Ahmad Sustainable Energy &Fuels.
2020, 4, 6188-6195.

a) D. Molina, M. A. Ruiz-Preciado, F. Sadegh, M. João Álvaro-Martins, M. Grätzel, A. Hagfeldt, Á. Sastre-Santos, J. Porphyr. Phthalocyanines, 2019, 23, 546–553. b) D. Molina, M. A. Ruiz‐Preciado, B. Carlsen, F. T. Eickemeyer, B. Yang, N. Flores‐Díaz, M. J. Álvaro‐Martins, K. Nonomura, A. Hagfeldt and Á. Sastre‐Santos, ChemPhotoChem, 2020, 4, 307–314.

a) L. Caliò, J. Follana-Berná, S. Kazim, M. Madsen, H. G. Rubahn, Á. Sastre-Santos, S. Ahmad, Sustainable Energy Fuels, 2017, 1, 2071-2077. b) P. Huang, A. Hernández, J. Follana-Berná, S. Kazim, J. Ortíz, Á. Sastre-Santos, S. Ahmad, ACS Appl. Energy Mater.
2021, 4, 9, 10124–10135

Figure 1
C3N4 and C3N5 Nanosheets As Passivation Layers and Carrier Extractors for Inorganic Semiconductor Nanowires and Quantum Dots
Authors: Alam Kazi , Kumar Pawan , Laishram Devika , Jensen Charles , Degg Annabelle , Chaulagain Narendra , Hegmann Frank , Nilges Tom , Sharma Rakesh , Shankar Karthik 
Published: July 2022

Inorganic semiconductor nanowires and quantum dots made of chalcogenides, III-V semiconductors and halide perovskites offer exciting potential for optoelectronic devices. The orthogonalization possible in nanowires between the normally competing processes of charge generation and charge separation have been used to project very high operating performance exceeding that of thin films and single crystals in light harvesting devices such as solar cells, photodetectors, photocatalysts and photoelectrolyzers. Likewise, inorganic quantum dots with size-tunable absorption and emission spectra are excellent candidates for light emitting devices as well as light harvesting devices. However, the practical performance of inorganic nanowire based optoelectronic devices has significantly lagged theoretical predictions. A major reason for the discrepancy between theory and experiment is the presence of surface traps and defects in nanowires and quantum dots, which exhibit a large surface area to volume ratio. Several chemical treatments and annealing regimens have been employed to heal surface defects in nanowires and quantum dots. One popular strategy involves wrapping nanowires and/or quantum dots with a thin coating of a molecular monolayer (e.g. alkanethiols) or an atomic layer deposited conformal oxide. While such core-shell architectures are frequently effective in reducing surface defects, the surface passivation is invariably accompanied by a deterioration in optoelectronic properties due to the difficulty experienced by charge carriers in tunneling through the thin shell layer. The resulting trade-off between surface passivation and carrier extraction limits performance improvements in light harvesting devices. Thus there is a strong need for passivating layers that do not negatively impact carrier extraction.
Herein, we show that graphitic carbon nitride coatings are highly effective in passivating the surfaces of inorganic nanowires and quantum dots while preserving excellent carrier transport and extraction. Three illustrative examples are provided together with in-depth spectroscopic and electrical characterization:
(1) Cesium lead bromide (CsPbBr3) quantum dots passivated by g-C3N4 nanosheets and performing spectacularly as CO2 photoreduction catalysts and water-splitting photoanodes
(2) The double helical ternary semiconductor SnIP passivated by g-C3N4 nanosheets which experienced a remarkable improvement in photoelectrochemical performance
(3) Cadmium sulfide (CdS) nanowires passivated by C3N5 nanosheets resulting in a superior photocatalytic performance
(Digital Presentation)Room Temperature Sensor Using Dielectrophoretic Trapping of Carbon Nanotubes
Authors: Ghomian Taher , Burdette Kaylee , Farimand Samaneh , Hihath Josh 
Published: July 2022

This abstract presents the design and fabrication of a temperature sensor based on carbon nanotubes (CNTs). The sensor is fabricated by dielectrophoretic trapping of CNTs between two nanoelectrodes. The conductance of the sensor is highly sensitive to the temperature variation which makes it suitable for applications requiring accurate measurements. In addition, fast response and good stability and durability are the important advantages of the sensors made of CNTs.
The structure of the device is shown in the figure. CNTs are trapped in between nanoelectrodes using the dielectrophoresis (DEP) technique. Dielectrophoresis is a phenomenon in which a force is applied to a dielectric particle when it is exposed to a non-uniform electric field [1]. Although dielectrophoresis provides an accurate method for trapping materials in a predefined area, this method suffers from a costly fabrication process when dealing with nanomaterials. In this study, we used a standard photolithography method to fabricate low-cost devices and an electronic circuit is used to apply the required electric field and monitor the gap for the presence of CNTs.
The device fabrication process starts with the patterning and depositing gold nanoelectrodes and contacts using the photolithography method. The process is followed by converting the surface of the device except for the nanoelectrodes area and connection pads with an insulation layer of Silicon nitride. Since the electrodes are thin (50 nm) and CNTs are flexible, fabrication on the flexible substrates is also feasible.
References
[1] T. Ghomian et al., "High‐Throughput Dielectrophoretic Trapping and Detection of DNA Origami," Advanced Materials Interfaces, vol. 8, no. 5, p. 2001476, 2021.

Figure 1
Bulk Heterojunction Solar Cells: Porphyrins, Dpps and Bodipys As Building Blocks for Efficient Donor Materials
Authors: Gros Claude , Bucher Léo , Desbois Nicolas , Sharma Ganesh D 
Published: July 2022

Among the different types of organic semiconducting materials, porphyrins, DPPs and BODIPYs based small molecules and conjugated polymers have attracted high interest as efficient semiconducting organic materials for dye sensitized solar cells (DSSC) and bulk heterojunction (BHJ) organic solar cells. Interestingly, they offer a synergistic effect when used together within a material, this coming from high complementarities of their absorption spectra, adapted prerequisites in order to be efficient energy transfer partners, and suitable frontier orbitals energy levels. We have recently designed different porphyrins, DPPs and BODIPYs based electron donor small molecules/polymers for bulk heterojunction organic solar cells (Figure), and now report their synthesis as well as the study of their electrochemical, photophysical and photovoltaic properties.
The “Consulat Général de France à Québec” and the “Programme Samuel de Champlain 2015/2016” are acknowledged for funding. We are thankful to Prof. P. D. Harvey (Université de Sherbrooke, CA) for PhD co-supervising and photophysical measurements.
REFERENCES

Bucher, L.; Desbois, N.; Harvey, P. D.; Sharma, G. D.; Gros, C. P., Solar RRL
2017, 1 (12), 1700127.

Bucher, L.; Tanguy, L.; Fortin, D.; Desbois, N.; Harvey, P. D.; Sharma, G. D.; Gros, C. P., ChemPlusChem
2017, 82, 625-630 (Biofest special issue).

Bucher, L.; Desbois, N.; Harvey, P. D.; Gros, C. P.; Sharma, G. D., ACS Appl. Mater. Interfaces
2018, 10 (1), 992-1004.

Bucher, L.; Tanguy, L.; Desbois, N.; Karsenti, P.-L.; Harvey, P. D.; Gros, C. P.; Sharma, G. D., Solar RRL
2018, 2 (1), 1700168.

Figure 1
Conversion of Meso-Aryl Substituted Open-Chain Pentapyrroles to Sapphyrins: Synthesis and Electrochemistry
Authors: Desbois Nicolas , Pacquelet Sandrine , Rousselin Yoann , Shan Wenqian , Kadish Karl M. , Gros Claude 
Published: July 2022

Sapphyrin is a 22-π aromatic pentapyrrolic macrocycle containing one direct link and four bridging methine groups between five pyrrole subunits.1 This macrocycle is an early member of the group of “expanded porphyrins” and was obtained from a pentapyrrole, a byproduct in the synthesis of corroles. A series of open-chain pentapyrroles and sapphyrins with meso-tetraaryl groups were synthesized (Figure 1) and are characterized as to their electrochemistry and protonation reactions in nonaqueous media.2 The protonation-initiated conversion of pentapyrroles to sapphyrins upon oxidation was investigated and cyclic voltammetry was used to measure the redox potentials in CH2Cl2, PhCN, and/or pyridine (Py).
REFERENCES
1. V. J. Bauer, D. L. J. Clive, D. Dolphin, J. B. Paine, F. L. Harris, M. M. King, J. Loder, S. W. C. Wang, R. B. Woodward, J. Am. Chem. Soc. 1983, 105,6429-6436.
2. W. Shan, N. Desbois, V. Blondeau-Patissier, M. L. Naitana, V. Quesneau, C. P. Gros, Y. Rousselin, W. Huang, Z. Ou, K. M. Kadish, Chem. Eur. J.,
2017
, 23, 12833-12844.
Figure 1

Figure 1
Prussian Blue Analogues for Potassium-Ion Batteries: Application of Complementary Operando X-Ray Techniques
Authors: Le Pham Phuong Nam , Wernert Romain , Aquilanti Giuliana , Johansson Patrik , Monconduit Laure , Stievano Lorenzo 
Published: July 2022

In the last 5 years, potassium-ion batteries (PIBs) have been considered as a promising post-lithium-ion battery technology, much due to cost effectiveness and a variety of electrode materials available [1]. Prussian Blue Analogues (PBAs), with advantages such as simple synthesis, high capacity, and eco-friendliness, have gained a huge interest [2–4] and here we present a detailed study on the electrochemical mechanism of K
x
Mn2/3Fe1/3[Fe(CN)6]
y
.zH2O. We do this by combining complementary operando techniques: X-ray diffraction and X-ray absorption spectroscopy, supported by ex situ
57Fe Mössbauer spectroscopy. Chemometric analysis of the operando data allows us to follow the physico-chemical and structural evolution during electrochemical cycling, providing deeper understanding. From this, a reversible phase transition between monoclinic and cubic crystal structure was observed during the oxidation/reduction of Mn species. The local geometry information on Fe and especially Mn, as obtained from the EXAFS data analysis, serves to explain the volume expansion of the Fe–CN–M (M = Mn, Fe) framework during the extraction of potassium. This paves the way for optimizing the PBA composition for PIB application.

References

[1] T. Hosaka, K. Kubota, A.S. Hameed, S. Komaba, Research Development on K-Ion Batteries, Chem. Rev. 120 (2020) 6358–6466. https://doi.org/10.1021/acs.chemrev.9b00463.
[2] X. Jiang, T. Zhang, L. Yang, G. Li, J.Y. Lee, A Fe/Mn-Based Prussian Blue Analogue as a K-Rich Cathode Material for Potassium-Ion Batteries, ChemElectroChem. 4 (2017) 2237–2242. https://doi.org/10.1002/celc.201700410.
[3] A. Zhou, W. Cheng, W. Wang, Q. Zhao, J. Xie, W. Zhang, H. Gao, L. Xue, J. Li, Hexacyanoferrate-Type Prussian Blue Analogs: Principles and Advances Toward High-Performance Sodium and Potassium Ion Batteries, Adv. Energy Mater. 11 (2021) 1–35. https://doi.org/10.1002/aenm.202000943.
[4] K. Hurlbutt, S. Wheeler, I. Capone, M. Pasta, Prussian Blue Analogs as Battery Materials, Joule. 2 (2018) 1950–1960. https://doi.org/10.1016/j.joule.2018.07.017.