Review
Chemistry, Inorganic & Nuclear
Jean-Francois Longevial, Clemence Rose, Ludivine Poyac, Sebastien Clement, Sebastien Richeter
Summary: This review discusses the importance of porphyrins and N-heterocyclic carbenes in coordination and organometallic chemistry, highlighting their wide applications in metal complexes and catalysis, and specifically describing structural diversity, electronic interplay, and relevant applications in catalysis and biomedicine.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Sebastian Koniarz, Kinga Szydelko, Michal J. Bialek, Karolina Hurej, Piotr J. Chmielewski
Summary: A family of transition metal complexes based on meso-aryl-2-aza-21-carbaporphyrin (N-confused porphyrin, NCP) derivatives were synthesized and characterized. The chirality of these complexes was demonstrated by enantiomeric separation and analysis. Preliminary catalytic study showed the activity of iridium(III) ortho-metallated complexes in the N-heterocyclization of primary amines with diols.
Article
Chemistry, Inorganic & Nuclear
Ayelen F. Crespi, Daniel Vega, Ana L. L. Perez, Enrique Rodriguez-Castellon, Juan M. M. Lazaro-Martinez
Summary: Novel coordination compounds, including mono- and binuclear copper complexes and a zinc complex, were synthesized and studied to determine the chemical functionalization of the carbonyl group in N-methyl-2-imidazolecarboxaldehyde ligand. X-ray crystallography was used as an indispensable tool for the analysis, as the chemical identification of the functional group is challenging due to the NMR signal interference caused by copper ions. The study revealed the aldehyde and gem-diol forms of the imidazole ligands in copper complexes, and the presence of gem-diol and carboxylate moieties in the crystal lattice of the zinc complex.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Erik T. Ouellette, Julian S. Magdalenski, Robert G. Bergman, John Arnold
Summary: We report the synthesis and characterization of a novel rhenium-group 9 heterobimetallic diazenido species and its related diazenido and hydride complexes. Furthermore, we demonstrate the possibility of N-C bond formation in heterobimetallic complexes and investigate their properties using spectroscopy and computational studies.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jia-Ling Yin, Meng-Ru Yin, Guo-Ping Yong
Summary: Two new coordination polymers and two novel isostructural metal-organic frameworks were synthesized using a new ligand. The dimensional and structural diversities were controlled by adjusting the solvent ratio, and enhanced luminescence emission was observed in certain frameworks.
Article
Chemistry, Inorganic & Nuclear
Hanhua Xu, Ze-Jie Lv, Junnian Wei, Zhenfeng Xi
Summary: A N-aryloxide-amidine ligand (H3L) was synthesized from 2-(aminomethyl)-6-(tert-butyl)phenol in two steps, which integrates phenoxide and amidine ligands through methylene linkers. The coordination modes of the resulting complexes depend on the radius of the metal ions. The ligand can form a dimer (LMIV-Cl)2 with group 4 metal chloride (MCl4)-Cl-IV, and the coordination mode of the amidinate moiety can change from bidentate chelating to bimetallic bridging coordination.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Yuji Mikata, Ayaka Takekoshi, Minori Kaneda, Shizuka Yonemura, Yuri Aono, Arimasa Matsumoto, Hideo Konno, Shawn C. Burdette
Summary: Fluorescence detection of Zn2+ and Cd2+ remains significant in biological and environmental sciences, but discriminating between the two ions has been a challenge. This study introduces three fluorescent probes with different responses to Zn2+ and Cd2+, providing a new approach for selective detection of these metal ions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Vasileios Filippou, Martina Bubrin, Anita Grupp, Mark R. Ringenberg, Wolfgang Kaim
Summary: The structures and spectroelectrochemical properties of compounds obtained from the reactions of different ligands with copper(I) and copper(II) precursors were studied. The copper(I) compounds showed different coordination modes and redox properties, while the copper(II) compounds exhibited diverse coordination modes. The spectroelectrochemistry also provided insights into their oxidation and reduction properties.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Multidisciplinary
Yoshihiro Ishimaru, Fumiya Takahashi, Samu Mochizuki, Natsuki Hosoda, Takashi Fujihara
Summary: In this study, two isomeric bis(dicarbonylrhodium(I)) complexes, one with a syn configuration and the other with an anti configuration, were successfully isolated and characterized. The analysis revealed significant differences in their structures and properties.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yuki Oka, Hiroshi Masai, Jun Terao
Summary: In this study, a ligand-controlled switching method for multistate switching of catenanes controlled by complexation with added amine ligands was reported. A [3]catenane with rigid pi-system comprised of cyclic porphyrin dimers was synthesized to verify this method. The relative positions among the cyclic components of the [3]catenane could be precisely controlled by complexation with various amine ligands. Furthermore, ligand-controlled multistate switching affected the optical properties of the [3]catenanes, with emission intensity being tuned by modulating the sizes and coordination numbers of integrated amine ligands. This work demonstrates the utility of using organic ligands for structural switching of catenanes and contributes to the development of multistate switchable mechanically interlocked molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Michael Doemling, Tom E. Stennett, Andrey Belyaev, Benjamin Hupp, Christina Claes, Stefan Ullrich, Sebastian Endres, Emely Freytag, Thomas Kramer, Thomas Kupfer, Fabian Schorr, Torsten Thiess, Merle Arrowsmith, Andreas Steffen, Holger Braunschweig
Summary: Nine different coinage metal pi complexes of diborenes with various anionic diborene and metal substituents were synthesized and characterized. Their optical properties were investigated to gain insights into the excited-state behavior and structure-property relationships. Structural and electronic modifications greatly influence the absorption, photostability, and quantum yields.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Zhi Wang, Mo Ashafaq, Yu-Fan Lu, Lei Feng, Mohamedally Kurmoo, Hongzhi Liu, Zhi-Yong Gao, Yun-Wu Li, Di Sun
Summary: Layering AgNO3 in alcohol onto octavinylsilsesquioxane (OVS) in CHCl3 results in a one-dimensional coordination polymer, consisting of unprecedented flat weakly bonded Ag-4(NO3)(4) alternating with the firmly covalent OVS through Ag-1-pi(C=C) bonds. The preferential assembling medium for SD/Ag4a is proven to be alcohols, where a 4:1 silver-OVS adduct is detected by electrospray ionization mass spectrometry. These outcomes provide insights into the specific interactions for supramolecular architectures of a polynuclear silver system built from OVS containing eight pendent olefin tails.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Venkata Sai Sashankh Penki, Yu-Lun Chang, Hsing-Yin Chen, Yu-Ting Chu, Yu-Ting Kuo, Dorothy Priyanka Dorairaj, Sri Sudewi, Shang-Wu Ding, Sodio C. N. Hsu
Summary: Two classes of beta-thioketiminate ligands were prepared to study their coordination behavior in copper(i) complex formation. The formation of copper(i) complexes with these ligands and their reaction with isocyanide, PPh3, and CO was investigated to address two important issues: the effect of denticity on copper(i) thiolate species formation and the influence of the length of the pendant pyridyl arm on coordination and reactivity behaviors. Based on characterization results, it was found that the denticity of the ligands influenced the nuclearity of copper(i)-thiolate species. FTIR measurements confirmed the coordination modes of the pendant pyridyl arm, indicating that the electron donating ability of the LCu fragment follows the order of SNN-chelator (SNN bound) > SNN-chelators (SN bound) > SN-chelator.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Valentina Ferraro, Filippo Baggio, Jesus Castro, Marco Bortoluzzi
Summary: Tetrahedral Zn(II) complexes with specific halide derivatives were synthesized and their structures were confirmed by single-crystal X-ray diffraction. The bromo- and iodo-derivatives exhibited luminescence properties upon excitation with light below 300 nm, with relatively long excited state lifetimes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jia-Hang Wu, Chun-Li Hu, Ting-Kun Jiang, Jiang-Gao Mao, Fang Kong
Summary: An ordered transition metal fluoroantimonite, K2SbMoO2F7, with high birefringence has been synthesized using the cationic size effect of alkali metals. The compound exhibits excellent transparency in the mid infrared range, making it a promising material for birefringent applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Tomoya Ishizuka, Shogo Tanaka, Sayaka Uchida, Lianyu Wei, Takahiko Kojima
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Hiroaki Kotani, Hinatsu Shimomura, Kei Ikeda, Tomoya Ishizuka, Yoshihito Shiota, Kazunari Yoshizawa, Takahiko Kojima
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Review
Chemistry, Physical
Takahiko Kojima
Summary: Nickel complexes have been studied as catalysts for visible-light-driven photocatalytic CO2 reduction for a long time. In contrast to Ru catalysts, nickel catalysts are important for CO2 reduction due to high selectivity in CO formation.
Article
Chemistry, Multidisciplinary
Sudhir Kumar Keshri, Tomoya Ishizuka, Takahiko Kojima, Yoshitaka Matsushita, Masayuki Takeuchi
Summary: This study reports the solution and solid-state studies of conformationally flexible multidecker naphthalenediimides (NDIs), revealing the existence of specific pi interactions in discrete pi-stacks. An unusual observation of a ten-electron reduction process in higher congeners was found, paving the way for designing multidecker pi-stacks with specific electronic properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Tomoya Ishizuka, Yuta Saegusa, Takahiko Kojima
Summary: Push-pull derivatives of zinc(II) complexes with quadruply fused porphyrinato ligands were synthesized to study the effect of push-pull on the electronic structure of the ligands. These derivatives showed charge-transfer bands sensitive to solvent polarity, due to extended pi-conjugation reaching the substituted positions. In contrast, push-pull derivatives of tetraphenylporphyrin, with disconnected pi-conjugation at certain bond positions, did not exhibit CT transitions from the substituents.
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
(2021)
Article
Chemistry, Organic
Tomoya Ishizuka, Takahiko Kojima
Summary: In recent years, functional molecules with expanded pi-conjugation circuits have gained attention for their potential in constructing optoelectronic materials. Among these molecules, porphyrin derivatives with ring-fused structures at the periphery have attracted attention due to their unique optoelectronic characteristics. This manuscript provides a brief overview of the synthesis and properties of ring-fused porphyrin derivatives reported since 2010.
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN
(2022)
Review
Chemistry, Inorganic & Nuclear
Tomoya Ishizuka, Hideki Sugimoto, Shinobu Itoh, Takahiko Kojima
Summary: Ruthenium and osmium complexes play crucial roles in oxidation reactions, generating high-valent species through peroxide activation and proton-coupled electron transfer. These complexes provide insights into oxidation mechanisms and exhibit unique reactivity.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Tomoya Ishizuka, Takahiko Kojima
Summary: This manuscript surveys the synthesis and properties of porphyrin derivatives with fused five-membered rings at the periphery. These derivatives exhibit unique properties, such as expanded aromatic and anti-aromatic circuits passing through the outer rim of the fused rings.
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
(2023)
Article
Multidisciplinary Sciences
Hiroto Fujisaki, Tomoya Ishizuka, Hiroaki Kotani, Yoshihito Shiota, Kazunari Yoshizawa, Takahiko Kojima
Summary: Efficient oxidation of alkanes, especially methane, is essential for using natural gas as chemical feedstock. Current industrial processes use high-temperature and high-pressure steam reforming to generate a gas mixture that can be further converted into products like methanol. However, this study demonstrates a new strategy using N-heterocyclic carbene-ligated Fe-II complexes to capture hydrophobic methane substrate from an aqueous solution, oxidize it to hydrophilic methanol, and release it back into the solution. By increasing the size of the hydrophobic cavities, the effect can be enhanced, achieving a turnover number of 5.0 x 10(2) and a methanol selectivity of 83% during a 3-hour methane oxidation reaction.
Article
Chemistry, Multidisciplinary
Tomoya Ishizuka, Atsushi Hosokawa, Takuya Kawanishi, Hiroaki Kotani, Yipeng Zhi, Takahiko Kojima
Summary: The promise of artificial photosynthesis in solving environmental and energy issues has sparked intensive research into photocatalytic systems for CO2 reduction. This study focuses on a dinuclear Ru-II complex that acts as a self-photosensitizing catalyst, demonstrating high efficiency and durability in CO2 reduction to produce CO.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Tomoya Ishizuka, Taichi Kogawa, Chisato Ogawa, Hiroaki Kotani, Yoshihito Shiota, Kazunari Yoshizawa, Takahiko Kojima
Summary: We synthesized and characterized a Ru-II-OH2 complex and studied its coordination equilibrium and oxidation reaction. The complex exhibits η6 coordination and intramolecular hydrogen bonding, which are important for catalytic oxidation reactions.
Review
Chemistry, Physical
Hiroto Fujisaki, Takahiko Kojima
Summary: This article surveys recent progress in the efficient and selective functionalization of methane using molecular metal complexes as catalysts. The reactions involve C-H bond cleavage by high-valent metal-oxo complexes and C-H bond activation at lower-valent metal centers, resulting in the formation of C-O or C-C bonds through oxygen-rebound, reductive elimination or insertion processes. The importance of hydrophobic environments around metal centers to improve the efficiency and product selectivity of CH4 oxidation is also discussed.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Hiroto Fujisaki, Masaya Okamura, Shiro Hikichi, Takahiko Kojima
Summary: Fe(ii) complexes with pentadentate ligands, including N-heterocyclic carbene moieties, were immobilized onto perfluorinated mesoporous aluminosilicate. These heterogeneous catalysts exhibited excellent performance and selectivity in alkane hydroxylation and cyclohexene epoxidation using H2O2 as the oxidant in CH3CN solvent.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Tomoya Ishizuka, Nitika Grover, Christopher J. Kingsbury, Hiroaki Kotani, Mathias O. Senge, Takahiko Kojima
Summary: This article summarizes the synthetic methods and design aspects of nonplanar porphyrin formation, the key properties and functionality of the nonplanar aromatic framework, and the scope and utility of this emerging class in addressing important scientific, industrial, and environmental issues.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Materials Science, Biomaterials
Haruka Araki, Shota Hagiwara, Ryosuke Shinomiya, Atsuya Momotake, Hiroaki Kotani, Takahiko Kojima, Takuro Ochiai, Naohiko Shimada, Atsushi Maruyama, Yasuhiko Yamamoto
Summary: The study found that the formation of an interpolyelectrolyte complex between heme-DNAzyme and a cationic copolymer with protonated amino groups can enhance the catalytic activity of heme-DNAzyme. This enhancement is attributed to the acid catalysis of protonated amino groups in the polymer, facilitating the formation of Compound I intermediate and improving the activity of heme-DNAzyme. Additionally, the enhancement of heme-DNAzyme activity by the polymer is dependent on factors such as the local heme environment and substrate accessibility to the heme.
BIOMATERIALS SCIENCE
(2021)