Article
Chemistry, Multidisciplinary
Biswajit Mondal, Soumitra Dinda, Neeta Karjule, Sanjit Mondal, Alagar Raja Kottaichamy, Michael Volokh, Menny Shalom
Summary: Electrolysis of water is a sustainable method to produce clean hydrogen, but it requires a high applied potential due to the pH-dependency of the hydrogen and oxygen evolution reactions. By combining proton-coupled electron transfer and single-electron transfer processes, we have achieved hydrogen production from water at low cell potentials by pH adjustment.
Article
Chemistry, Multidisciplinary
Yusuke Yoneda, S. Jimena Mora, James Shee, Brian L. Wadsworth, Eric A. Arsenault, Diptarka Hait, Gerdenis Kodis, Devens Gust, Gary F. Moore, Ana L. Moore, Martin Head-Gordon, Thomas A. Moore, Graham R. Fleming
Summary: This study investigates the photoinduced PCET dynamics of a biomimetic model system using various spectroscopic techniques and computational methods, providing insights into the complex dynamics and synergistic motions involved in the process. Specifically, the evolution of the 2DEV line shape, sensitive to the mixing of vibronic states, is interpreted through accurate computational modeling of the charge separated state, revealing a gradual change in electron density distribution associated with a dihedral twist occurring on a 120 fs time scale.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Multidisciplinary Sciences
Zhongneng Zhou, Zijing Chen, Xiu-Wen Kang, Yalin Zhou, Bingyao Wang, Siwei Tang, Shuhua Zou, Yifei Zhang, Qiaoyu Hu, Fang Bai, Bei Ding, Dongping Zhong
Summary: In this study, the photocycle of the FMN-Gln-Tyr motif in the BLUF domain of OaPAC was investigated using computational simulations. The results show that forward PCET is concerted, while only the wild-type protein proceeds with an ultrafast reverse PCET process.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Multidisciplinary
Clorice R. Reinhardt, Elvira R. Sayfutyarova, Jiayun Zhong, Sharon Hammes-Schiffer
Summary: Ribonucleotide reductase (RNR) is an essential enzyme in DNA synthesis, with the active form of E. coli Ia RNR consisting of two subunits, alpha and beta, involved in a series of proton-coupled electron transfer (PCET) reactions. Quantum mechanical/molecular mechanical simulations suggest thermodynamically favored forward radical transfer in the pre-turnover state and backward radical transfer in the post-turnover state between Y731 and Y730. The simulations also propose that E623 plays a key role in influencing the directionality of PCET and predict the impact of mutation of E623 on catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Quantum Science & Technology
Jonas Mielke, Jason R. Petta, Guido Burkard
Summary: Nuclear spins exhibit long coherence times and strong isolation from the environment, making them promising for quantum information applications. A method for nuclear spin readout by probing microwave resonator transmission is presented, demonstrating feasibility with current state-of-the-art devices. Optimal readout points with strong signal contrast and potential for coherent excitation exchange between a nuclear spin qubit and cavity photons are identified.
Article
Electrochemistry
Jean-Francois Longevial, Iryna Knysh, Shaymaa Al Shehimy, Lhoussain Khrouz, Aramugam Pandurangan, Simon Pascal, Gabriel Canard, Christophe Bucher, Denis Jacquemin, Olivier Siri
Summary: Researchers have synthesized and characterized the soluble 6,13-dipivaloyl-5,14-dihydro-5,7,12,14-tetraazapentacene and its aromatic counterpart. Using complementary chemical, (spectro)-electrochemical, theoretical, and spectroscopic techniques, all the intermediates generated during the electrochemical processes of these compounds were fully characterized. The results demonstrate the ambipolar redox behavior of 6,13-dipivaloyl-5,14-dihydro-5,7,12,14-tetraazapentacene, leading to drastic color changes through proton-coupled electron transfer in a totally reversible fashion.
ELECTROCHIMICA ACTA
(2023)
Article
Chemistry, Physical
Mayra Peralta, Steven Feijoo, Solmar Varela, Rafael Gutierrez, Gianaurelio Cuniberti, Vladimiro Mujica, Ernesto Medina
Summary: We investigate the role of electron-spin-phonon coupling in DNA using an effective model Hamiltonian and its connection to the Chiral-Induced Spin Selectivity (CISS) effect. The semiclassical electron transfer in a tight-binding model of DNA with intrinsic spin-orbit coupling is described using the envelope function approach. We find that only acoustic modes exhibit spin-phonon coupling, while optical modes show electron-phonon interaction without spin coupling. An effective Hamiltonian is derived, in which the eigenstates carry spin currents protected by spin-inactive stretching optical modes. The stronger interaction between optical phonons and electrons allows for the decoherence effects and the spin filtering effects observed in CISS.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Pinit Ariyageadsakul, Kyoung Koo Baeck
Summary: The charge-transfer excited state of NH3Cl can undergo a typical proton-coupled electron transfer process through proton transfer and electron transfer. The study reveals that the branching ratio is influenced by the vibration levels of the initial precursor anion and the isotope substitution of the connecting H atom.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Wencong Sun, Dong Yao, Yuehua Tai, Li Zhou, Wenxue Tian, Min Yang, Chunxiang Li
Summary: Polyoxometalates (POMs) can effectively catalyze the electrocatalytic CO2 reduction reaction (CO2RR) through multistep proton-coupled electron transfer (PCET) processes. In this study, a combination of commercial indium electrodes with Keggin-type POMs (PVnMo(12-n)O40)(n+3)- (n = 1, 2, 3) achieved a Faradaic efficiency toward ethanol of 93.4% at -0.3V (vs. RHE). The PCET processes in POMs activated CO2 molecules and caused the oxidation of the electrode, resulting in the loss of active sites. The addition of POM electrolyte additives regulated the interface microenvironment and improved CO2RR performance.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Nanoscience & Nanotechnology
Junji Fujimoto, Florian Lange, Satoshi Ejima, Tomonori Shirakawa, Holger Fehske, Seiji Yunoki, Sadamichi Maekawa
Summary: By utilizing response theory, the paper calculates the charge current vortex generated by spin pumping at a point-like contact in a system with Rashba spin-orbit coupling. The oscillatory behavior of the charge current as a function of distance from the spin pumping source is observed, which is supported by numerical simulations. The introduction of the SOC Hamiltonian on the lattice as the generator of the spin current is a significant aspect of their calculations.
Review
Chemistry, Physical
Feng Zhu, Wenbin Zhang, Jiao Xun, Bi-Jun Geng, Qing-Man Liang, Yang Yang
Summary: This review focuses on the effects of proton donor/acceptor on several typical electrocatalytical reactions, including species, concentration, pKa, and steric hindrance. Specifically, the proton transfer pathway arising from ligand design strategy of molecular catalysts and modification of electrode-electrolyte interface is presented.
CURRENT OPINION IN ELECTROCHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Belinda Pettersson Rimgard, Zhen Tao, Giovanny A. Parada, Laura F. Cotter, Sharon Hammes-Schiffer, James M. Mayer, Leif Hammarstrom
Summary: In this study, a photochemical mechanism termed proton-coupled energy transfer (PCEnT) was experimentally discovered and theoretically analyzed. Anthracene-phenol-pyridine triads were found to undergo a local excited state and emit fluorescence through singlet-singlet energy transfer, despite the lack of spectral overlap. Theoretical calculations also indicated negligible charge transfer between the anthracene and phenol-pyridine units. These findings suggest the relevance of PCEnT in biological systems and future photonic devices.
Article
Nanoscience & Nanotechnology
Yuanfeng Gao, Qingyu Xue, Jiayuan Li, Mingkai Zhang, Yuanyuan Ma, Yongquan Qu
Summary: Coupling acid-electrolyte proton exchange membrane fuel cells with cathodic hydrogenation shows potential in energy and chemical industry. The use of phytate coordination on Cu surface enhances the kinetic of proton adsorption/activation and hydrogenation activity. This work provides a promising approach to integrate electricity generation and chemical production.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Physical
Rong-Zhen Liao, Jing-Xuan Zhang, Zhenyang Lin, Per E. M. Siegbahn
Summary: QM/MM calculations were used to investigate the reduction of acetylene to ethylene catalyzed by the DCCPCh enzyme with an [Fe8S9] double-cubane cluster. Various reaction pathways involving different oxidation states and protonation states were analyzed to find the most favorable one. The reaction proceeds via a special double-electron transfer induced proton transfer mechanism with the anti-ferromagnetically coupled [Fe8S8] cluster delivering electrons to the substrate.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Ananta Dey, Nandan Ghorai, Amitava Das, Hirendra N. Ghosh
Summary: This study investigates the effects of H-bonding on PET and PCET processes. The results show that the presence of an intramolecular H-bond significantly increases the rate of electron transfer from Ru(II) to AQ. Additionally, the study demonstrates the ultrafast electron transfer and PCET dynamics in the presence of water and highlights the significant role of the bi-imidazole spacer and water molecules in both PET and PCET.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ryojun Toyoda, Naoya Fukui, Dionisius H. L. Tjhe, Ekaterina Selezneva, Hiroaki Maeda, Cedric Bourges, Choon Meng Tan, Kenji Takada, Yuanhui Sun, Ian Jacobs, Kazuhide Kamiya, Hiroyasu Masunaga, Takao Mori, Sono Sasaki, Henning Sirringhaus, Hiroshi Nishihara
Summary: This study investigates the use of mixed nickel and copper ions to fabricate coordination nanosheet films based on benzenehexathiolato (BHT). It is found that this heterometallicity results in improved crystallinity and electrical conductivities in the films. Spectroscopic and scattering measurements confirm the formation of a bilayer structure with larger and more oriented grains. These findings open new opportunities for improving the functional properties of 2D coordination nanosheets.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Yohei Hattori, Ryota Kitajima, Ryota Matsuoka, Tetsuro Kusamoto, Hiroshi Nishihara, Kingo Uchida
Summary: The luminescence of stable radicals can be enhanced by coordination to metal complexes. The fluorescence quantum yield of F2PyBTM radical in dichloromethane was increased from 4% to 36% by coordination to Au-I metal complex with N-heterocyclic carbene ligand, setting a record for metal-radical complexes.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Tetsuro Kusamoto, Chie Ohde, Shiori Sugiura, Satoshi Yamashita, Ryota Matsuoka, Taichi Terashima, Yasuhiro Nakazawa, Hiroshi Nishihara, Shinya Uji
Summary: In this study, a newly synthesized organic quantum spin liquid (QSL) was investigated for its structure and physical properties. The antiferromagnetic interaction in this QSL was found to be smaller than that in other organic QSLs, while the chi(0) and gamma values were larger. The results provide evidence of the spinon Fermi surface in the QSLs.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Article
Chemistry, Multidisciplinary
Joe Komeda, Kenji Takada, Hiroaki Maeda, Naoya Fukui, Takuya Tsuji, Hiroshi Nishihara
Summary: Recent studies have mainly focused on the discovery of new precursors for molecular 2D materials with high tunability of structure and function. This study demonstrates a facile one-pot synthesis of laminated 2D coordination polymer films and provides insights into their structure and charge transfer properties. The bilayer film shows stable rectification character in a dry condition.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Dong Xia, Ken Sakaushi, Andrey Lyalin, Keisuke Wada, Sonu Kumar, Marco Amores, Hiroaki Maeda, Sono Sasaki, Tetsuya Taketsugu, Hiroshi Nishihara
Summary: This study demonstrates the potential of bis(diimino)copper framework for reversible multielectron transfer in electrochemical energy storage. An experiment-theory collaboration reveals the importance of cation-anion interactions in non-oxide abundant electrode systems. It is found that the copper-nitrogen bonds undergo a unique reversible rearrangement during lithium intercalation, leading to significant multielectron transfer. This research provides new insights into affordable multielectron transfer electrodes and presents an alternative strategy for advancing electrochemical energy storage reactions.
Review
Chemistry, Inorganic & Nuclear
Ryota Matsuoka, Asato Mizuno, Takuto Mibu, Tetsuro Kusamoto
Summary: This review discusses open-shell luminescent molecular systems with spin doublet ground states, including organic radicals, radical-ligated metal complexes, and metal complexes with magnetic metal ions. These molecular systems exhibit unique luminescent properties and have promising applications in various light functional applications.
COORDINATION CHEMISTRY REVIEWS
(2022)
Review
Chemistry, Inorganic & Nuclear
Hiroaki Maeda, Kenji Takada, Naoya Fukui, Sayoko Nagashima, Hiroshi Nishihara
Summary: This review focuses on electrically conductive coordination nanosheets (CONASHs) and summarizes recent progress regarding their structural diversity, synthesis, conductive properties, and applications as energy storage materials, electrocatalysts, and sensors. It concludes with future perspectives.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Materials Science, Multidisciplinary
Hwan-Hee Cho, Shun Kimura, Neil C. Greenham, Yuki Tani, Ryota Matsuoka, Hiroshi Nishihara, Richard H. Friend, Tetsuro Kusamoto, Emrys W. Evans
Summary: Fluorescent organic radicals with doublet-spin energy levels can overcome efficiency limits in OLEDs from singlet-triplet photophysics, potentially improving performance. By utilizing electron donor-acceptor mixed hosts to control charge transport, the optoelectronic performance of radical OLEDs can be enhanced.
ADVANCED OPTICAL MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Ryota Matsuoka, Shojiro Kimura, Tomoaki Miura, Tadaaki Ikoma, Tetsuro Kusamoto
Summary: Luminescent radicals are a new class of materials with unique photofunctions due to their open-shell electronic structure. Of particular interest are photofunctions where the radical's spin and luminescence are correlated, such as magnetoluminescence (ML), which can be useful in spin photonics. This study demonstrates that a covalently linked luminescent radical dimer can exhibit ML as a single-molecular property, providing insights into the requirements and mechanisms of ML in radicals and aiding the design of ML-active radicals through synthetic chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Inorganic & Nuclear
Tetsuya Kambe, Hiroshi Nishihara, Kimihisa Yamamoto
Summary: This article presents a chemical bottom-up approach for synthesizing single-atomic-layered materials like graphene, focusing on borophene-oxide and metalladithiolene layers. These inorganic materials have graphene-like two-dimensional networks that allow for introducing functionalities, and their atomically thin layers can be obtained through dissolution or synthetic methods. The article also evaluates their two-dimensional electronic features, such as the anisotropic characteristics of borophene-oxide layers and the switching abilities of metalladithiolene layers. Evaluating its importance, I would give a rating of 9 out of 10.
DALTON TRANSACTIONS
(2023)
Article
Polymer Science
Hiroaki Maeda, Kenji Takada, Naoya Fukui, Junzo Ukai, Nobutaka Honma, Sono Sasaki, Hiroyasu Masunaga, Kenichi Kato, Hiroshi Nishihara
Summary: Multilayered coordination nanosheets composed of copper ions and hexaaminobenzene (CuHAB) were synthesized through a liquid-liquid interfacial reaction. The study found that an appropriate oxidizing agent and quantitative addition of base can modulate the chemical structure, crystal structure, and conductivity of the synthesized nanosheets.
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS
(2023)
Article
Materials Science, Multidisciplinary
Yohei Hattori, Ryota Matsuoka, Atsumi Baba, Kohei Yamamoto, Ryota Matsuoka, Tetsuro Kusamoto, Kingo Uchida
Summary: Eight new stable luminescent radicals are reported, and the luminescent properties of these radicals can be controlled by changing the hydrocarbon substituents.
MATERIALS ADVANCES
(2023)
Article
Chemistry, Multidisciplinary
Yohei Hattori, Ryota Kitajima, Wataru Ota, Ryota Matsuoka, Tetsuro Kusamoto, Tohru Sato, Kingo Uchida
Summary: In this study, a donor-radical acceptor system was developed by adding an alkylbenzene to a diphenylpyridylmethyl radical acceptor. The resulting system showed high fluorescence efficiency, which was attributed to the molecular arrangement and control of structural relaxation.
Article
Materials Science, Multidisciplinary
Sara Mattiello, Yohei Hattori, Ryota Kitajima, Ryota Matsuoka, Tetsuro Kusamoto, Kingo Uchida, Luca Beverina
Summary: In this study, quadruple addition of phenyl groups to a diphenylpyridylmethane skeleton was achieved, leading to the synthesis of a radical with superior luminescence properties. Further modifications with different functional groups resulted in the isolation of other compounds. These radicals not only exhibited excellent fluorescence properties, but also showed improved photostability.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
