Article
Multidisciplinary Sciences
Ryunosuke Hayashi, Shohei Tashiro, Masahiro Asakura, Shinya Mitsui, Mitsuhiko Shionoya
Summary: The structure of porous molecular crystals can be controlled allosterically by the adsorption of effectors within low-symmetry nanochannels with multiple molecular recognition sites, leading to diverse framework structure conversion and switchable molecular affinity at different recognition sites. These findings may provide guidance for the development of supramolecular materials with flexible and highly-ordered three-dimensional structures for biological applications.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Inorganic & Nuclear
Koji Yamamoto, Tsuyoshi Sugawa, Tetsuro Murahashi
Summary: This review summarizes the coordination behavior of fused benzene ring hydrocarbons (FBHs) in di- or multinuclear metal complexes, particularly focusing on their coordination modes to multinuclear metal moieties.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Sohyun Park, Jiung Jang, Yuya Tanaka, Hyo Jae Yoon
Summary: This paper describes the thermoelectric properties of molecular junctions incorporating multinuclear ruthenium alkynyl complexes. High Seebeck coefficients and thermal stability were observed, providing important insights into the development of molecular-scale devices for efficient thermoregulation and heat-to-electricity conversion.
Review
Chemistry, Inorganic & Nuclear
Mostafa Khoshsefat, Yanping Ma, Wen-Hua Sun
Summary: The aim of designing multinuclear catalysts for olefin polymerization is to control the catalyst behavior and final polymer properties, with the length and nature of the linker playing a key role in metal center adjacency and cooperative interactions. Late transition metal catalysts are attractive due to their structure and behavior, leading to increased interest in multinuclear catalysts.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Biochemistry & Molecular Biology
Maria Incoronata Nardella, Mariagrazia Fortino, Alessandra Barbanente, Giovanni Natile, Adriana Pietropaolo, Fabio Arnesano
Summary: This study investigates the metal binding mechanism of the copper transporter Ctrl using a 14mer peptide corresponding to its N-terminal region. The peptide contains specific motifs that can bind Cu(II)/Ni(II) and Cu(I)/Ag(I) ions. The results show that the peptide can bind one or two metal ions in the same or different oxidation states at neutral pH. Lowering the pH to 3.5 causes the detachment of Cu(II) ions from the peptide, making them susceptible to reduction to Cu(I). Cu(I) ions stably bind to the peptide at low pH. DFT calculations support the easy interconversion of monovalent cations between different coordination modes.
FRONTIERS IN MOLECULAR BIOSCIENCES
(2022)
Article
Chemistry, Inorganic & Nuclear
Daniela Lalli, Ivan Hawala, Marco Ricci, Fabio Carniato, Luca D. D'Andrea, Lorenzo Tei, Mauro Botta
Summary: The GdAAZTA complex is a promising platform for MRI probe design due to its magnetic properties, stability, and versatility. In this study, derivatives of GdAAZTA functionalized with different amino acids were synthesized and characterized. The results showed that functionalization with amino acids maintained the hydration state of the complex and improved its relaxivity. The new complexes also exhibited excellent chemical stability in biological matrices.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Bishnu Das, Parna Gupta
Summary: Square planar Pt(II) complexes were reported as luminescent biosensors for DNA detection, with the bright red photoluminescence induced by aggregation serving as the sensing mechanism. The study explored terpyridine-appended geminal bistriazoles for metal coordination, resulting in tetranuclear and dinuclear Pt(II) complexes with different ligand environments. This is the first report of terpyridine-appended geminal bistriazoles in the literature.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Shinnosuke Horiuchi, Hirotaka Hiroiwa, Eri Sakuda, Yasuhiro Arikawa, Keisuke Umakoshi
Summary: This study reports the formation and photophysical properties of two types of sandwich complexes supported by asymmetric Pt complex units with different acetylide groups. The asymmetric Pt complex unit was obtained through the acetylide metathesis reaction between two types of symmetric Pt complexes. The incorporation of Cu ions effectively suppressed the reversible acetylide exchange reaction, resulting in the formation of unique chiral Pt4Cu3 and achiral Pt2Cu4Br4 sandwich complexes. The sandwich complexes exhibited moderate photoluminescence in the solid state, and their photophysical properties were dependent on the sandwich structures. These results indicate that remarkable assembled structures can be achieved by asymmetric Pt complex units through the concerted effect of labile coordination bonds and weak noncovalent interactions.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Inorganic & Nuclear
Kazuki Tanifuji, Shun Ohta, Yasuhiro Ohki, Hidetake Seino
Summary: Metal-sulfur (M-S) clusters are a class of multi-metallic compounds with high affinity, forming various compounds with different nuclearities. Recent biochemical studies have elucidated the structures of native M-S clusters, allowing us to develop artificial catalysts superior to enzymes and for biologically inaccessible reactions. This review summarizes the progress in the reaction studies on synthetic M-S clusters for the activation and transformation of small molecules.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Takuo Minato, Masahiro Sadakane
Summary: A cationic metal glue strategy utilizing lacunary-type polyoxometalates (POMs) as rigid multidentate ligands is demonstrated for increasing the size and nuclearity of hetero-multinuclear metal-oxo clusters. The method enabled the synthesis of {(FeMn4)Mn2Ln2(FeMn4)} oxo clusters (Ln=Gd, Tb, Dy, and Lu), which are currently the largest reported paramagnetic hetero-multinuclear metal-oxo clusters in POMs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Environmental Sciences
Tuantuan Fan, Xin Yao, Haoyu Ren, Feiyang Ma, Li Liu, Xiaojia Huo, Tong Lin, Haiyan Zhu, Yinghao Zhang
Summary: This study investigated the spatial differences in compositions, molecular weight structures, and binding mechanisms between dissolved organic matter (DOM) and copper (Cu2+) in Dongping Lake. The results showed that the DOM in the lake exhibited specific differences in space, components, and molecular weights, which have significant implications for understanding the behavior and bioavailability of heavy metals in lakes.
ENVIRONMENTAL POLLUTION
(2022)
Article
Chemistry, Multidisciplinary
Matteo Mauro
Summary: In recent years, multimetallic compounds have emerged as a valuable alternative in the field of luminescent transition metal complexes research. The multimetallic strategy has been proven highly suitable for compounds emitting efficiently in the challenging red to near-infrared region, leading to improved optical properties.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Chengjie Sun, Zhaoxuan Yang, Peng Wu, Xiangjie Luo, Kun Liu, Binju Wang, Hongyu Lin, Jinhao Gao
Summary: In this study, multinuclear Mn(II) united-DOTA chelates are shown to have higher inertness and efficiency compared to Gd-based contrast agents. The unusual inertness is attributed to the multiplexed uniting of Mn(II) chelates, as demonstrated by controlled studies on model compounds. In vivo experiments further demonstrate that Mn(II) united-DOTA complexes provide more substantial and persistent contrast enhancement than both Mn-DOTA and Magnevist.
CELL REPORTS PHYSICAL SCIENCE
(2022)
Review
Biochemistry & Molecular Biology
Linda Biro, Peter Buglyo, Etelka Farkas
Summary: This review highlights the long-standing tradition and diverse applications of natural and synthetic hydroxamic acids and their derivatives, emphasizing their role as effective metal-chelating agents in medicinal practice. The importance of understanding the stoichiometry, binding modes, and thermodynamic parameters of metal complexes with hydroxamic acid-based ligands is crucial for scientists working in related fields. Additionally, the review discusses the factors affecting the metal-binding capabilities of these organic ligands and explores the possibilities for quantitative comparison of their effectiveness and selectivity through solution equilibrium data.
CURRENT MEDICINAL CHEMISTRY
(2021)
Article
Engineering, Environmental
Zhenqing Shi, Qianting Ye, Yang Ding, Zecong Ding, Rong Li
Summary: Soil dissolved organic matter (DOM) is a complex mixture of organic compounds in soil solutions, which has a significant impact on various biogeochemical processes in the soil environment. However, the relationship between the chemical complexity of soil DOM molecules and their proton and metal binding abilities is still unclear, limiting our ability to predict the behavior of DOM and metals in the environment. In this study, we developed a modeling approach to quantify the proton and metal binding abilities of soil DOM, based on Cu titration experiments, Fourier transform ion cyclotron resonance mass spectrometry data, and molecular modeling methods. Despite the heterogeneity and diversity of soil DOM properties in samples from different regions, we were able to classify the molecules into three representative groups based on their Cu binding capacity. By developing molecular models for each group and considering their relative contributions in each soil DOM sample, we could predict the molecular properties and binding abilities of soil DOM as a whole. These findings will contribute to the development of mechanistic models for predicting the reactivity of soil DOM from different sources.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Shinnosuke Horiuchi, Keisuke Umakoshi
Summary: This review summarizes the progress in developing two types of unique luminescent supramolecular systems, including heteronuclear complexes involving heterometallic metal-metal interactions and host-guest systems consisting of mononuclear metal complexes and a hydrogen-bonded capsule.
Article
Chemistry, Inorganic & Nuclear
Shinnosuke Horiuchi, Seiya Tanaka, Sangjoon Moon, Eri Sakuda, Akitaka Ito, Yasuhiro Arikawa, Keisuke Umakoshi
Summary: The synthesis and photophysical properties of the heteropolynuclear Pt-Ag complex with cyclometalated rollover bipyridine ligands and bridging pyrazolato ligands were reported. The Pt2Ag2 complex exists as a mixture of U- and Z-shaped isomers, with the ability to form Pt. Ag dative bonds and significantly change emission energy. The additional Ag(I) ion affects the photophysical properties of these complexes as revealed by DFT and TD-DFT calculations.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Shinnosuke Horiuchi, Sangjoon Moon, Akitaka Ito, Jacopo Tessarolo, Eri Sakuda, Yasuhiro Arikawa, Guido H. Clever, Keisuke Umakoshi
Summary: Multinuclear Ag clusters sandwiched by Pt complex units exhibit fluxional behavior and strong photoluminescence properties, with chiral enantiomers showing unprecedented circular dichroism and circularly polarized luminescence properties. Theoretical calculations help understand the structural features and photophysical properties of these complex molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Yasuhiro Arikawa, Motoki Yamada, Nobuko Takemoto, Shinnosuke Horiuchi, Eri Sakuda, Keisuke Umakoshi
Summary: The study revealed the kinetics of the insertion reaction between complex 2 and DMAP, including activation enthalpy, activation entropy, and Gibbs activation energy. The experimental results suggest the inclusion of both complex 2 and DMAP in the transition state.
Article
Chemistry, Multidisciplinary
Shinnosuke Horiuchi, Hirotaka Hiroiwa, Eri Sakuda, Yasuhiro Arikawa, Keisuke Umakoshi
Summary: This study reports the formation and photophysical properties of two types of sandwich complexes supported by asymmetric Pt complex units with different acetylide groups. The asymmetric Pt complex unit was obtained through the acetylide metathesis reaction between two types of symmetric Pt complexes. The incorporation of Cu ions effectively suppressed the reversible acetylide exchange reaction, resulting in the formation of unique chiral Pt4Cu3 and achiral Pt2Cu4Br4 sandwich complexes. The sandwich complexes exhibited moderate photoluminescence in the solid state, and their photophysical properties were dependent on the sandwich structures. These results indicate that remarkable assembled structures can be achieved by asymmetric Pt complex units through the concerted effect of labile coordination bonds and weak noncovalent interactions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Naoki Kitamura, Yuki Kurashige
Summary: This study examined the charge-ordered phase transition in (TMTTF)(2)MF6 systems by using an extended Hubbard model and confirmed that the strength of nearest-neighbor Coulomb interactions for this phase transition should be twice as much as previously obtained.
CHEMICAL PHYSICS LETTERS
(2022)
Article
Chemistry, Physical
Soichiro Nishio, Yuki Kurashige
Summary: We demonstrate the importance of dynamical electron correlation effect in diabatic electron-exchange processes in molecular aggregates. A multireference perturbation theory with a large active space is performed using an efficient low-rank approximation. It is found that the direct term of diabatic couplings is not sufficient to explain the kinetic rates of electron-exchange processes, such as singlet fission, triplet-triplet annihilation, and triplet exciton transfer, but these processes are efficiently mediated by low-lying charge transfer states if the two molecules are in close proximity. It is also observed that regardless of the distance between the molecules, the direct term is significantly underestimated without the dynamical electron correlation.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Kentaro Hino, Yuki Kurashige
Summary: The matrix product state formulation of the multiconfiguration time-dependent Hartree theory is extended to realistic anharmonic potentials with n-mode representations beyond the linear vibronic coupling model. It is confirmed that the use of local coordinates can significantly improve the efficiency of the method.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Inorganic & Nuclear
Shinnosuke Horiuchi, Yiming Yang, Misa Ueda, Eri Sakuda, Yasuhiro Arikawa, Keisuke Umakoshi
Summary: In this study, a rational synthesis of an unsymmetric Pt complex with two different pyrazole ligands was successfully carried out. The unsymmetric Pt complex was used to selectively form a Z-shaped Pt2Ag2 complex, whose structures were confirmed by X-ray crystallographic and NMR analysis. It was found that the steric effect of the pyrazole ligands determined the orientation of the Pt complex units, but had little influence on the photophysical properties of the complexes. TD-DFT calculations supported the small electronic contributions of the pyrazole moieties in the Pt and Pt2Ag2 complexes. This synthetic route offers a new strategy for obtaining new types of precious metal sandwich complexes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Witold M. Bloch, Shinnosuke Horiuchi, Julian J. Holstein, Christoph Drechsler, Axel Wuttke, Wolf Hiller, Ricardo A. Mata, Guido H. Clever
Summary: Helicity is an important structural motif in biological systems that contributes to molecular recognition in DNA. However, the relationship between helicity and guest encapsulation in artificial supramolecular hosts is not well understood. This study explores a coiled-up Pd2L4 metallohelicate and its tight anion binding capability, demonstrating that the coiled-up cage has an oblate/prolate cavity expansion that allows for strong host-guest interactions, confirmed by various analytical techniques.
Article
Multidisciplinary Sciences
Shinnosuke Horiuchi, Takumi Yamaguchi, Jacopo Tessarolo, Hirotaka Tanaka, Eri Sakuda, Yasuhiro Arikawa, Eric Meggers, Guido H. Clever, Keisuke Umakoshi
Summary: In this study, we achieved symmetry-breaking self-assembly of a defined C-1-symmetric supramolecular structure by the synergistic effects of weak binding forces. The flexible capsule framework undergoes a large structural change upon guest binding, forming a distorted resorcin[4]arene hexameric capsule with an asymmetric cavity. The location of the chiral guest in the anisotropic environment leads to modulation of its Electric Dipole (ED) and Magnetic Dipole (MD) transition moments, resulting in increased emission quantum yield and circularly polarized luminescence.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Irene Regeni, Rituparno Chowdhury, Kai Terlinden, Shinnosuke Horiuchi, Julian J. J. Holstein, Sascha Feldmann, Guido H. H. Clever
Summary: This article introduces a strategy to engineer the stacking of diketopyrrolopyrrole (DPP) dyes based on non-statistical metallosupramolecular self-assembly. Different discrete assemblies can be formed by adding Pd(II) to the DPP backbone equipped with nitrogen-based donors, distinguished by the number of π-stacked chromophores. We obtained and systematically investigated a Pd3L6 three-ring, a heteroleptic Pd2L2L’2 ravel composed of two crossing DPPs (flanked by two carbazoles), and two unprecedented self-penetrated motifs (a Pd2L3 triple and a Pd2L4 quadruple stack). With increasing counts of stacked chromophores, UV/Vis absorptions red-shift and emission intensities decrease, except for compound Pd2L2L’2, which has an exceptional photoluminescence quantum yield of 51% explainable by an intra-assembly FRET process. The modular design and synthesis of soluble multi-chromophore building blocks offer potential for the preparation of nanodevices and materials with applications in sensing, photo-redox catalysis, and optics.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yasuhiro Arikawa, Motoki Yamada, Nobuko Takemoto, Takuya Nagaoka, Yusuke Tsujita, Taiji Nakamura, Yusuke Tsuruta, Shinnosuke Horiuchi, Eri Sakuda, Kazunari Yoshizawa, Keisuke Umakoshi
Summary: Sulfite reduction is a crucial process in the global sulfur cycle, and it can be achieved using transition-metal complexes. In our study, we successfully simulated and achieved the stepwise reduction of sulfite from sulfite to sulfur monoxide, then to disulfide, and finally to hydrogen sulfide using a dinuclear ruthenium complex.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Inorganic & Nuclear
Shinnosuke Horiuchi, Mikihiro Hayashi, Keisuke Umakoshi
Summary: Molecular recognition of guest molecules in a confined cavity plays an important role in biological and artificial molecular systems. Resorcin[4]arene-based supramolecular hosts provide internal cavities that can accommodate coordination complexes, leading to the modulation of chemical and physical properties of the guests. By carefully selecting the host and guest complexes, a new supramolecular system can be created with unique structures and properties derived from the trapped coordination complexes.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Tsukasa Abe, Shinnosuke Horiuchi, Shuichi Hiraoka
Summary: In this study, we report the narcissistic self-sorted state achieved from two structurally similar tritopic ligands and a cis-protected Pd(ii) complex. The formation of this metastable state is influenced by the pathway-dependent process and the appropriate choice of the leaving ligand. Simple mixing and heating under thermodynamic control cannot produce this state.
CHEMICAL COMMUNICATIONS
(2022)
