Article
Chemistry, Organic
Mikhail A. Kalinin, Aleksei V. Medved'ko, Mikhail E. Minyaev, Sergey Z. Vatsadze
Summary: A new method for synthesizing N,N'-unsymmetrically substituted 9-aminobispidines has been developed using aminal bridge removal reaction, which allows selective functionalization of all three nitrogen atoms. The reaction intermediates and mechanism of the 1,3-diazaadamantane's aminal bridge removal reaction have been characterized and proposed. Novel saturated heterocyclic 1,5,9-triazatricyclo-[5.3.1.0(3,8)]-undecanes have been synthesized and structurally characterized. This study also successfully obtained 3,7,9-trisubstituted bispidines with acetyl, Boc, and benzyl groups at nitrogen atoms, which can be independently removed (orthogonal protective groups) for the first time.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jiwei Wang, Xiang Cheng, Ye Liu, Jun Zhang
Summary: A variety of novel chiral and achiral 4,5-disubstituted 1-aryl-3-alkyl-imidazolium salts were synthesized through multicomponent reactions. Additionally, two novel unsymmetrical bulky cycloalkyl-based NHC-Pd complexes exhibited high catalytic activity in Suzuki-Miyaura and Negishi cross-coupling reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Srinivas Anga, Himadri Karmakar, Tarun K. Panda, Vadapalli Chandrasekhar
Summary: The synthesis and characterization of alkali metal complexes of an unsymmetrical monoanionic imidazolin-2-imino-phosphanamidinate ligand were reported. The structures of lithium, sodium, and potassium complexes were established using single-crystal X-ray diffraction analysis, showing kappa(2) bonding to the ligand moiety.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
David Gomez de Segura, Nora Gimenez, David Rincon-Monton, M. Teresa Moreno, Jose G. Pichel, Iciar P. Lopez, Elena Lalinde
Summary: A new family of luminescent heteroleptic pentafluorophenyl-bis(2-phenylbenzothiazolyl) Pt-IV derivatives were designed and their photophysical properties were systematically studied. The cationic complexes 1-3 exhibited remarkable efficacy against lung carcinoma and cervix carcinoma cell lines. The neutral complex 6 showed low cytotoxicity and high photocytotoxicity when irradiated with blue light.
DALTON TRANSACTIONS
(2023)
Review
Biochemistry & Molecular Biology
Zufar N. Gafurov, Artyom O. Kantyukov, Alexey A. Kagilev, Alina A. Kagileva, Il'yas F. Sakhapov, Ilya K. Mikhailov, Dmitry G. Yakhvarov
Summary: Pincer complexes are important in organometallic chemistry, especially as homogeneous catalysts for organic transformations. Non-symmetrical phosphorus-based pincer nickel complexes have shown higher catalytic activity and have gained increasing attention in recent years. This mini-review focuses on the recent advances in the chemistry of these complexes, including ligand design, synthesis, and catalytic applications.
Article
Chemistry, Inorganic & Nuclear
Saray Argibay-Otero, Rosa Carballo, Ezequiel M. Vazquez-Lopez
Summary: Nine thiosemicarbazone ligands (HL) with S,N,Npy-tridentate coordination were synthesized and analyzed. Different types of compounds were obtained through the reactions of [ReX-(CH3CN)2(CO)3]/[ReX(CO)5] (X = Cl and Br) precursors with these ligands. The study also explored the influence of substituents on ligand stability and the effect of reaction medium on the resulting compounds.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Debsouri Kundu, Natalia del Rio, Marie Cordier, Nicolas Vanthuyne, Emma V. Puttock, Stefan C. J. Meskers, J. A. Gareth Williams, Monika Srebro-Hooper, Jeanne Crassous
Summary: The preparation, structural and spectroscopic characterization of the first enantiopure cycloplatinated complexes with a bidentate, helicenic N-heterocyclic carbene and a diketonate ancillary ligand were investigated through experimental and computational studies. These complexes exhibit long-lived circularly polarized phosphorescence, with dissymmetry factor g(lum) values >= 10(-3) in solution, doped films at room temperature, and around 10(-2) in a frozen glass at 77 K.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Medicinal
Tao Jia, Oumar Diane, Deepanjan Ghosh, Myriem Skander, Gaelle Fontaine, Pascal Retailleau, Joel Poupon, Jerome Bignon, Ytabelle Maga Moulai Siasia, Vincent Servajean, Nathalie Hue, Jean-Francois Betzer, Angela Marinetti, Sophie Bombard
Summary: This article introduces a new series of bimetallic platinum-(II) complexes with NHC-type bridging ligands, which exhibit cytotoxicity, cell accumulation, and DNA binding properties in cancerous cells. These complexes demonstrate significant radiosensitizing effects by inhibiting DNA repair mechanisms, leading to persistent accumulation of irradiation-induced DNA damages. This study provides the first in vitro evidence for the radiosensitizing properties of NHC-platinum complexes, suggesting their potential use in combined chemo-radiotherapy protocols.
JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Stefano Scoditti, Eslam Dabbish, Nino Russo, Gloria Mazzone, Emilia Sicilia
Summary: This study investigates the cytotoxicity and photophysical properties of a platinum complex containing a 2,6-dipyrido-4-methyl-benzene chloride ligand through density functional theory and molecular dynamics simulations. The complex is found suitable as a photosensitizer for photodynamic therapy, with evaluations on how DNA intercalation and binding affect sensitization activity.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Anna Farasat, Luca Labella, Fabio Marchetti, Simona Samaritani
Summary: Isocyanide ligands react with transition metal complexes to form corresponding complexes, and react with amines to form non-cyclic carbene addition products.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Inorganic & Nuclear
Katarzyna Wolska, Jan Janczak, Paula Gawryszewska, Jerzy Lisowski
Summary: A step-by-step synthesis was conducted to prepare enantiopure unsymmetrical macrocycles L-3 and L-4, containing two pyridine units and two different diamine and diimine links. The structures of these complexes were identified using 2D NMR, ESI MS spectroscopy, and X-ray crystallography, with luminescent properties of the Eu(III) complexes characterized.
Article
Chemistry, Inorganic & Nuclear
Katarzyna Mlodzikowska-Pienko, Bartosz Trzaskowski
Summary: Computational calculations reveal that the bimolecular coupling mechanism is the favored degradation pathway for cyclic (alkyl)(amino) carbenes (CAACs) and unsymmetrical N-heterocyclic carbenes (uNHCs) catalysts. These catalysts also exhibit higher stability compared to other common catalysts.
Article
Biochemistry & Molecular Biology
Thomas M. Kirse, Joschua Lueke, Ivan Maisuls, Alexander Hepp, Cristian A. Strassert
Summary: In this work, coordination compounds featuring caffeine-based carbene co-ligands and tridentate dianionic pincer luminophores were studied. The influence of different substituents on the photophysical properties was assessed. The results showed that the four luminophores performed similarly and cyclometallation improved the synthetic efficiency but was not essential for achieving high photoluminescence quantum yields. In summary, coordination chemical concepts based on natural products can lead to stable phosphorescent species with interesting excited-state properties.
PHOTOCHEMISTRY AND PHOTOBIOLOGY
(2023)
Article
Chemistry, Multidisciplinary
J. L. S. Milani, A. F. P. Biajoli, F. I. Batista, R. S. Oliboni, O. L. Casagrande
Summary: A series of new Cr(III) complexes were successfully synthesized and showed moderate activity in ethylene oligomerization, with a uniform distribution of oligomers and polymer production ranging from 1.2% to 9.8%. The catalytic activity is mainly controlled by electronic effects at the thioether/imine groups.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Ajay Padunnappattu, Carine Duhayon, Vincent Cesar, Yves Canac
Summary: In this study, a tricationic imidazolium salt with two N-cyclopropenio substituents was prepared using the onio-substitution strategy. The electronic properties of the related dicationic NHC were evaluated, and it was found to be one of the least-donating cationic NHCs reported so far. The ability of this compound to coordinate with Pd(II) and Au(I) centers was also investigated, and corresponding complexes were characterized.
Article
Materials Science, Multidisciplinary
Tomofumi Kadoya, Shotaro Mano, Aoi Hori, Keishiro Tahara, Kunihisa Sugimoto, Kazuya Kubo, Masaaki Abe, Hiroyuki Tajima, Jun-ichi Yamada
ORGANIC ELECTRONICS
(2020)
Article
Chemistry, Multidisciplinary
Takashi Ikeda, Keishiro Tahara, Tomofumi Kadoya, Hiroyuki Tajima, Noriaki Toyoda, Satoshi Yasuno, Yoshiki Ozawa, Masaaki Abe
Article
Chemistry, Multidisciplinary
Yoshiki Ozawa, Hiroki Iida, Hidetoshi Kiyooka, Kazutaka Nobori, Keishiro Tahara, Toshikazu Ono, Masaaki Abe
Summary: The new tetracopper(I) complex with a cuboidal Cu4S4 core has been synthesized and structurally characterized. The monoanionic iminothiolate ligand makes the cluster framework exceptionally stable in solution, allowing for examination of solution properties using various spectroscopic techniques.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2021)
Article
Chemistry, Multidisciplinary
Ken Tokunaga, Fumiya Odate, Daiya Asami, Keishiro Tahara, Mitsunobu Sato
Summary: The study simplified the molecular shapes for quantum-dot cellular automata, presenting a practical procedure to design molecules that can respond accurately to different electric field patterns and function correctly in logic gates.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2021)
Article
Chemistry, Physical
Sunao Shimomoto, Tomofumi Kadoya, Toshiaki Tanimura, Kazusuke Maenaka, Tokuji Yokomatsu, Takeshi Komino, Hiroyuki Tajima
Summary: This study investigated the charge injection barrier at the H2Pc/Pd interface using ACM, revealing a hole injection barrier of 0.26 eV and an electron injection barrier of 2.49 eV. Positive offset voltage allowed for the determination of band gap and electron injection barrier at the LUMO/Pd interface.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Crystallography
Tomofumi Kadoya, Shiori Sugiura, Toshiki Higashino, Keishiro Tahara, Kazuya Kubo, Takahiko Sasaki, Kazuo Takimiya, Jun-ichi Yamada
Summary: This study reports the structural and physical properties of a new organic Mott insulator (BEDT-BDT)AsF6, revealing that at low temperatures, the AsF6 salt causes an increase in angle between BEDT-BDT molecules, leading to a significant change in the electronic structure.
Article
Chemistry, Multidisciplinary
Keishiro Tahara, Shun Takezaki, Yoshiki Ozawa, Masaaki Abe
Summary: This study reports the synthesis and characterization of a novel alkyl-Co(III) complex that enables C-H functionalization through C(sp(3))-H bond activation. The complex shows a unique coordination geometry and exhibits good reactivity and stability.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Article
Chemistry, Multidisciplinary
Tomofumi Kadoya, Masaharu Shishido, Shiori Sugiura, Toshiki Higashino, Keishiro Tahara, Kazuya Kubo, Takahiko Sasaki, Jun-ichi Yamada
Summary: A new organic donor BEDT-BDS with a greater degree of molecular bending compared to BEDT-BDT has been synthesized, forming a quasi-one-dimensional electronic structure in a radical-cation salt.
Article
Chemistry, Multidisciplinary
Takashi Ikeda, Keishiro Tahara, Ryoichi Ishimatsu, Toshikazu Ono, Luxia Cui, Momoka Maeda, Yoshiki Ozawa, Masaaki Abe
Summary: This study presents a method for stabilizing electrogenerated radical ions by effectively decorating organic donor-acceptor diads with B(C6F5)(3). By employing the p-type organic semiconductor benzothienobenzothiophene (BTBT) as the donor, tetracoordinate boron complexes show improved solution electrochemiluminescence (ECL) intensity. The Lewis-pairing-induced ECL enhancement is attributed to the multiple roles of B(C6F5)(3) in redistributing frontier orbitals, facilitating electrochemical excitation, and restricting molecular motions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Sonomi Arata, Yuna Kim, Norihisa Hoshino, Keishiro Tahara, Kiyonori Takahashi, Tomofumi Kadoya, Tomonori Inoue, Takayoshi Nakamura, Tomoyuki Akutagawa, Jun-ichi Yamada, Kazuya Kubo
Summary: Unsymmetrical ppy-gold(III) complexes coordinated by dithiolene ligands with pentylthio and hexylthio groups were synthesized. The complexes formed one-dimensional columnar structures in crystals with head-to-tail molecular arrangements around the metal ions. [AuC5] exhibited a simple phase transition between crystalline and isotropic phases irreversibly at 198°C, while [AuC6] melted at 148°C and slowly crystallized to a different crystalline phase above 148°C, which transformed into an isotropic phase at 200°C.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Keishiro Tahara, Yuya Ashihara, Takashi Ikeda, Tomofumi Kadoya, Jun-ichi Fujisawa, Yoshiki Ozawa, Hiroyuki Tajima, Noriaki Toyoda, Yuichi Haruyama, Masaaki Abe
INORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Tomofumi Kadoya, Shiori Sugiura, Keishiro Tahara, Toshiki Higashino, Kazuya Kubo, Takahiko Sasaki, Kazuo Takimiya, Jun-ichi Yamada