Article
Chemistry, Multidisciplinary
Leland B. Gee, Jinkyu Lim, Thomas Kroll, Dimosthenis Sokaras, Roberto Alonso-Mori, Chien-Ming Lee
Summary: We utilized hard X-ray spectroscopic methods to identify the structural features and reaction mechanisms of two photolabile {FeNO}(6) complexes, providing a foundation for future research.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Leland B. Gee, Jinkyu Lim, Thomas Kroll, Dimosthenis Sokaras, Roberto Alonso-Mori, Chien-Ming Lee
Summary: In this study, hard X-ray spectroscopic methods were used to investigate the structural features of two photolabile {FeNO}(6) complexes. The presence of a pendant thiol or thioether was found to affect the ability of the complexes to generate HNO. The findings of this study are important for future research on these systems and other challenging redox systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Aniruddha Dey, Therese Albert, Richard Y. Kong, Samantha N. MacMillan, Pierre Moenne-Loccoz, Kyle M. Lancaster, David P. Goldberg
Summary: This study reports the generation of N2O in a nonheme complex upon addition of NO. A metastable FeNO intermediate was trapped and characterized by low-temperature spectroscopic studies. Thermal decay of the FeNO species was found to result in the evolution of N2O, without the requirement of any exogenous electron or proton sources.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Aniruddha Dey, Jesse B. Gordon, Therese Albert, Sinan Sabuncu, Maxime A. Siegler, Samantha N. MacMillan, Kyle M. Lancaster, Pierre Moenne-Loccoz, David P. Goldberg
Summary: A new nonheme iron(II) complex was reported, which reacts with NO(g) to form a stable mononitrosyl complex. The mononitrosyl complex exhibits highly activated characteristics and can rapidly convert to N2O in the absence of an exogenous reductant.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Shankhadeep Saha, Sayani Maity, Rakesh Mazumdar, Bapan Samanta, Riya Ghosh, Ankur K. Guha, Biplab Mondal
Summary: Nitroxyl and nitroxide anions are the reduced forms of nitric oxide and have distinct advantages in pharmacology and therapy. However, the role of nitroxyl in chemical biology is not as extensively studied as nitric oxide. Metal nitrosyl complexes can serve as efficient nitroxyl donors, overcoming the limitations of existing examples.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Fei-Yan Chen, Jian-Rong Li, Xu-Feng Liu, Pei-Hua Zhao
Summary: In this study, two new ethanedithiolate complexes were synthesized and characterized. The results showed that these complexes exhibited electrocatalytic activity for the reduction of protons to hydrogen in the presence of acetic acid.
JOURNAL OF COORDINATION CHEMISTRY
(2022)
Article
Chemistry, Physical
Polina Topchiyan, Andrey Komarovskikh, Irina Yushina, Vladislav Komarov, Danila Vasilchenko, Sergey Korenev
Summary: This study investigates the solid state photolysis of (Bu4N)(2)[Pt(NO3)(6)] salt, and discovers the formation of a paramagnetic Pt(III) complex [Pt(NO3)(5)]( 2- ) through the reduction of Pt(IV) centers under irradiation at 455 nm and shorter wavelengths. Prolonged irradiation or aging in the dark leads to the formation of mixed-valence Pt(III)-Pt(IV) species from trapped [Pt(NO3)(5)] (2- ) and [Pt(NO3)(6)](2-) anions.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2022)
Article
Chemistry, Physical
Qin Huang, Ping Yu, Li-Hua He, Jing-Lin Chen, Sui-Jun Liu, He-Rui Wen
Summary: Two new monometallic copper(I) complexes have been synthesized and characterized, showing improved luminescence properties. The introduction of electron-donating methyl groups on the 6-cyano-2,2'-bipyridine ligands is favorable for enhancing the luminescence properties of the Cu(I) complexes.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Multidisciplinary
Hai T. Dong, Stephanie Camarena, Debangsu Sil, Michael O. Lengel, Jiyong Zhao, Michael Y. Hu, E. Ercan Alp, Carsten Krebs, Nicolai Lehnert
Summary: In this study, a new model system for flavodiiron nitric oxide reductases (FNORs) was reported, which can mediate direct nitric oxide (NO) reduction or stabilize the first intermediate of the reaction. The results demonstrate that the high-spin {FeNO}7 complexes require a higher activation level for NO reduction compared to those in FNORs, highlighting the importance of hydrogen bonding residues in the active sites of FNORs.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Yashwant Bhaskar Pandit, Yan-Ting Jiang, Jia-Jyun Jian, Tai-Chi Chen, Tung-Chun Kuo, Mu-Jeng Cheng, Rai-Shung Liu
Summary: This study reports the gold-catalyzed [5 + 2]-annulations using commonly used anthranils and 1,3-diynamides to produce quinoline oxides, with the improved chemoselectivity attributed to the electron-withdrawing effects of aryltosylamides and alkynes.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Daisuke Saitoh, Ayumi Suzuki, Naoya Ieda, Zuoyue Liu, Yasuko Osakada, Mamoru Fujitsuka, Mitsuyasu Kawaguchi, Hidehiko Nakagawa
Summary: We have developed photocontrollable NO-releasing molecules that can be used in biological experiments and therapy. The NO-generating system involves intermolecular photoredox reaction between separate components and is activated by purple or blue light, releasing NO.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jang-Hoon Cho, Minyoung Kim, Youngmin You, Hong-In Lee
Summary: A new photoactivable NO-releasing ruthenium nitrosyl complex, [Ru(EPBP)Cl(NO)], with a distorted octahedral coordination geometry and NO positioned at cis to Cl- ion, was synthesized and its photodissociation characterized using various techniques. Experimental and theoretical investigations indicate that the EPBP2- ligand serves as an effective platform for forming ruthenium nitrosyl complexes useful for NO-photoreleasing.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Huai-Cheng Chen, Gene-Hsiang Lee, Su-Ying Chien, Chien-Ming Lee
Summary: NO production can be effectively achieved through photolysis and organic compounds with pendant thiol/thioether groups. The Fe-NO bond in these iron-nitrosyl-thiolato complexes is weakened by light exposure, and the noncovalent SH of 1 or SCH3 of 2 can act as incoming ligands to interact with the Fe atom, facilitating NO dissociation.
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Minyoung Kim, Seongchul Park, Dayoon Song, Youngmin You, Manho Lim, Hong-In Lee
Summary: In this study, the influence of substitution on NO photolysis and NO-releasing dynamics was investigated by introducing the electron-donating group (-OH) to the aromatic rings of Ru(salophen)(NO)Cl complex. The results showed that the introduction of hydroxyl groups elevated the ligand pi-bonding orbitals and decreased the HOMO-LUMO gaps, leading to a decrease in the quantum yields of NO photolysis.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Sergey P. Gromov, Timofey P. Martyanov, Artem I. Vedernikov, Svetlana N. Dmitrieva, Dmitry V. Kondratuk, Artem P. Vorozhtsov, Evgeny N. Ushakov
Summary: E-isomers of styryl dyes containing a benzo-18-crown-6 ether or N-methylbenzoaza-18-crown-6 ether moiety and a benzothiazolium residue with an ammoniohexyl, ammoniopentyl, or ammoniomethylbenzyl N-substituent were synthesized. According to spectrophotometry and NMR spectroscopy data, dyes of this type are capable of self-assembly in MeCN to form dimeric complexes, which have a pseudocyclic structure owing to double intermolecular ammonium cation-crown ether interactions via hydrogen bonds; the dimerization equilibrium constants were measured. It was shown that photoinduced Z-isomers of the dyes are capable of intramolecular complex formation between the ammonium cation and the crown ether moiety; therefore, upon E -> Z photoisomerization, the dimer-monomer equilibrium shifts towards the pseudocyclic monomer. Data on the relative stability of the intramolecular cation-capped complexes formed by Z-isomers were obtained. It was shown that the equilibrium constants for the Ba2+ complexation with E-isomers of the dyes are almost three orders of magnitude higher than those for that with Z-isomers, which may imply the applicability of these dyes as photoswitchable supramolecular devices.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yang Liu, Stefan G. G. Resch, Haowei Chen, Sebastian Dechert, Serhiy Demeshko, Eckhard Bill, Shengfa Ye, Franc Meyer
Summary: This article describes a flexible macrocyclic ligand that can host two Cu ions in reversibly interconvertible states. The complexes were characterized using various spectroscopic methods and calculations. The electron self-exchange between the two states is rapid despite structural reorganization and is proposed to proceed via an active conformer. This redox couple is unique and achieves fast electron self-exchange similar to the function of the Cu-A site.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Kui Zeng, Claudia Stueckl, Jie Qin, Martin Simon, Can-Jerome Spyra, Jun Li, Franc Meyer, Kai Zhang
Summary: This article reports a highly efficient iodoarene-mediated aerobic oxidation method for carboxylic acids in aqueous phase, which provides access to a large number of carboxylic acids containing aromatic aldehydes and saturated/unsaturated aliphatic aldehydes. Detailed mechanistic studies provide strong evidence for the interception of hypervalent iodine intermediates through aldehyde hydrate.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Luisa Maria Gatzemeier, Franc Meyer, Ulf Diederichsen, Tiago Fleming Outeiro
Summary: Alpha-Synuclein is a protein involved in neurodegenerative disorders that accumulate in brain protein inclusions. We have developed a chemical synthesis method for Alpha-Synuclein, allowing the synthesis of protein variants for further investigation of its structure and aggregation behavior.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Ruth Weller, Mihail Atanasov, Serhiy Demeshko, Ting-Yi Chen, Ivan Mohelsky, Eckhard Bill, Milan Orlita, Franc Meyer, Frank Neese, C. Gunnar Werncke
Summary: The magnetic properties of linear iron(I) silylamides K{crypt}[FeL2] and [KFeL2] were investigated. Slow-relaxation of magnetization, magnetic hysteresis, and magnetic blocking were observed in K{crypt}[FeL2]. In [KFeL2], with increased axial anisotropy, higher relaxation barrier and blocking temperature were observed, in agreement with field-dependent IR-spectroscopy, magnetic measurements, and theoretical analysis.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ting Yi Lai, Chang-Ting Chen, Kai-Ti Chu, Su-Ying Chien, Tiow-Gan Ong, Ming-Hsi Chiang
Summary: A new 3Fe4S cluster related to M-cluster of Mo-nitrogenase is reported. It is synthesized from the structural rearrangement of [K(THF)(2)][(mu,kappa(2)-bdt)Fe-2(mu-PPh2)(CO)(5)] under visible light irradiation. The Fe-hydride species (1H) with bridging hydride group is generated and characterized by H-1-NMR spectroscopy and DFT calculation. Complex 1 exhibits reversible reduction and oxidation processes in CH3CN solution.
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jakob Steube, Ayla Kruse, Olga S. Bokareva, Thomas Reuter, Serhiy Demeshko, Roland Schoch, Miguel Arguello A. Cordero, Athul Krishna, Stephan Hohloch, Franc Meyer, Katja Heinze, Oliver Kuehn, Stefan Lochbrunner, Matthias Bauer
Summary: This study presents a luminescent iron compound that exhibits dual emission behavior from ligand-to-metal charge transfer (LMCT)- and metal-to-ligand charge transfer (MLCT)-dominated states. The compound has a unique ligand design that enables the presence of energetically accessible MLCT states, providing potential for electron transfer reactions in photoredox catalysis.
Article
Chemistry, Physical
Tim P. Schlachta, Greta G. Zambo, Michael J. Sauer, Isabelle Rueter, Carla A. Hoefer, Serhiy Demeshko, Franc Meyer, Fritz E. Kuehn
Summary: A comparative study was conducted to investigate the influence of electronic variations on the catalytic performance of three iron(II) NHC epoxidation catalysts. Different ligands were used to prepare the complexes, which were characterized using various methods. The results showed that a lower electron density at the iron atom led to a decline in epoxidation activity, while a more electron rich iron center did not necessarily result in higher activity due to reduced catalyst stability. Addition of Lewis acids significantly improved both activity and stability of the catalysts.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Yang Liu, Sayanti Chatterjee, George E. Cutsail III, Sergey Peredkov, Sandeep K. Gupta, Sebastian Dechert, Serena DeBeer, Franc Meyer
Summary: This study reports the synthesis and characterization of [Cu-4(& mu;(4)-S)](n+) (n = 2, 2; n = 3, 3) clusters, which mimic the two active states of the Cu-Z* site during enzymatic N2O reduction. The structural and electronic properties of these clusters are elucidated using multiple methods. Preliminary reactivity studies demonstrate the nucleophilic character of the central & mu;(4)-S in the fully reduced 0-hole state.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Hao-Wen Kang, Yu-Chiao Liu, Wei-Kai Shao, Yu-Chen Wei, Chi-Tien Hsieh, Bo-Han Chen, Chih-Hsuan Lu, Shang-Da Yang, Mu-Jeng Cheng, Pi-Tai Chou, Ming-Hsi Chiang, Yao-Ting Wu
Summary: The synthesis, structures, and properties of highly twisted alkenes were investigated. The rotation of the central C = C bonds in these compounds is as facile as the rotation of aryl-aryl bonds in 2-fluorobiphenyl. The compounds exhibit broad photoabsorption range, reduced HOMO-LUMO gap, and small singlet-triplet energy gap.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jose de Jesus Velazquez-Garcia, Krishnayan Basuroy, Darina Storozhuk, Joanne Wong, Serhiy Demeshko, Franc Meyer, Robert Henning, Simone Techert
Summary: This study investigates the structural evolution of a defect [2 x 2] triiron(II) metallogrid during temperature increase and light irradiation. The flexibility of the grid leads to interesting characteristics that can be used for intermolecular cooperativity in related thermally responsive systems. The time-resolved photocrystallography reveals the photoinduced and elastic steps in the out-of-equilibrium process.
DALTON TRANSACTIONS
(2023)
Article
Materials Science, Multidisciplinary
Weiyang Li, Aurelian Rotaru, Mariusz Wolff, Serhiy Demeshko, Franc Meyer, Yann Garcia
Summary: By symmetric modification of the ligand architecture, two iron-based complexes were constructed as colorimetric NH3(g) sensors, which showed a remarkable colour change from reddish brown or light purple to dark grey at room temperature. One of the complexes presented a shorter response time due to its empty cage structure and large specific surface area increasing the adsorption rate of NH3(g).
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Sandeep K. Gupta, Shashank V. Rao, Serhiy Demeshko, Sebastian Dechert, Eckhard Bill, Mihail Atanasov, Frank Neese, Franc Meyer
Summary: Understanding the effects of the local coordination environment and ligand field on magnetic anisotropy is crucial for controlling the magnetic properties of single-ion magnets (SIMs). In this study, a series of tetracoordinate cobalt(ii) complexes with electron-withdrawing -C6F5 substituents were synthesized and their magnetic properties were investigated. The results showed that the dihedral twist angle between the chelate planes in the solid state greatly influenced the magnetic properties, and the energy gaps of electronic transitions were correlated with the zero-field splitting (ZFS) parameter.
Article
Chemistry, Inorganic & Nuclear
Gargi Bhatt, Tanu Sharma, Sandeep K. Gupta, Franc Meyer, Gopalan Rajaraman, Ramaswamy Murugavel
Summary: In this study, the single-ion magnetic (SIM) behavior of three mononuclear cobalt-(II) tetrahedral complexes was examined. The variation in the dynamic magnetic properties of the Co-(II) ion in a tetrahedral ligand field was studied by changing the halide ligand. The ab initio CASSF calculations matched well with the experimental data, revealing the influence of halide ions on the axial zero-field splitting parameter D.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Weiyang Li, Xiaochun Li, Koen Robeyns, Mariusz Wolff, Joseph Kfoury, Julianna Olah, Radovan Herchel, Serhiy Demeshko, Franc Meyer, Yann Garcia
Summary: In this study, two new types of edge-bridged spin crossover supramolecular cages were constructed, and their magnetic properties were investigated in the presence of different solvents and anions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Andres Gonzalez, Serhiy Demeshko, Franc Meyer, C. Gunnar Werncke
Summary: A labile iron organoazide adduct that undergoes dissociation equilibrium and intramolecular C-H bond amination in solution is reported. Single-crystal irradiation of the azide led to the formation of a putative imido iron intermediate, identified as a highly covalent {FeNR}8 species computationally.
CHEMICAL COMMUNICATIONS
(2023)
