Article
Chemistry, Multidisciplinary
Takumi Nukazawa, Takeaki Iwamoto
Summary: The compound with unsupported bridgehead Si-Si pi bond and ethynyl pi moieties was successfully synthesized, and effective pi conjugation between the unsupported Si-Si pi and ethynyl pi units was observed.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Ashanul Haque, Khalaf M. Alenezi, Muhammad S. Khan, Wai-Yeung Wong, Paul R. Raithby
Summary: The design and development of functional materials with practical applications require high standards. Understanding and controlling inter- and intra-molecular interactions offer opportunities for designing new materials. Manipulating the molecular structure can significantly alter these interactions and enhance the properties and functions of the material. Non-covalent interactions (NCIs) have been found to have beneficial effects, indicating that manipulating NCIs can generate functional materials with various physical properties for applications in catalysis, drug delivery, crystal engineering, etc. This review aims to explore the implications of NCIs on molecular packing, optical properties, and applications of functional pi-conjugated materials. Additionally, it attempts to delineate the effects of weak interactions on opto-electronic (O-E) applications.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Yun Xiong, Shicheng Dong, Shenglai Yao, Chenshu Dai, Jun Zhu, Sebastian Kemper, Matthias Driess
Summary: White phosphorus (P-4) undergoes degradation to produce 2,5-disila-3,4-diphosphapyrrole 2 and two novel functionalized Si=P doubly bonded compounds 3 and 4 when exposed to the new N,N-bis(silylenyl)aniline PhNSi2 1. The transformation of compound 2 into compounds 3 and 4 can be achieved depending on the molar ratio of 1 and P-4 as well as the reaction conditions. These compounds can interconvert through reactions with 1 and P-4.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Energy & Fuels
Xin Li, Chengyi Xiao, Zhaofan Yang, Hao Wang, Baiqiao Liu, Wen Liang Tan, Qiaomei Chen, Chao Wang, Christopher R. McNeill, Weiwei Li
Summary: In this study, three double-cable conjugated polymers were developed for indoor single-component organic solar cells (SCOSCs). The new polymers have pendent nonfused electron acceptors with A-pi-D-pi-A configuration, using 1H-indene-1,3(2H)-dione (ID) as an electron-withdrawing end group in group A. These polymers show absorption spectra in the range of 400-700 nm, matching the spectra of indoor LED lights. Additionally, the introduction of ID units and halogen atoms enables the polymers to exhibit high photovoltage (>1.0 V) in SCOSCs, resulting in a high efficiency of 18% under indoor light illumination. This research provides a novel modular design approach for wide-bandgap double-cable conjugated polymers that can be used for indoor photovoltaics.
Article
Chemistry, Inorganic & Nuclear
Mohd Nazish, Christina M. Legendre, Nico Graw, Regine Herbst-Irmer, Shahila Muhammed, Pattiyil Parameswaran, Dietmar Stalke, Herbert W. Roesky
Summary: This study presents a method for preparing chain-type unsaturated molecules with low oxidation state Si(I) and Sb(I), and their characteristics of sigma-type lone pairs and pseudo-pi bonds are investigated. The formation of the pseudo-pi bond is through the hyperconjugative transfer of the pi-type lone pair at Sb to the Si-N sigma* MO.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Anna-Lena Thoemmes, Bernd Morgenstern, Michael Zimmer, Diego M. Andrada, David Scheschkewitz
Summary: Heavier tetrylenes have potential in synthesis, catalysis, and small molecule activation. Coordination by N-heterocyclic carbenes (NHCs) and cyclic (alkyl)(amino)carbenes (CAACs) results in structural and electronic differences. NHC-coordination to bridged bis(germylene) results in pyramidal germanium centers with lone pairs of electrons, while CAAC-coordination results in an unprecedented stable bis(germene) with two Ge=C bonds. The coordination of NHC is reversible, providing a low-temperature route towards polymers with Ge=Ge bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Energy & Fuels
Fang Fang, Zhi-Ting Gong, Li-Feng Yao, Wen Pu, Yu-Qing Cai, Qi-Ling Li, Jian-Jun Liu, Shu-Biao Xia
Summary: In this work, 2D porous covalent quinazoline organic network (CQN) materials were synthesized with abundant mesoporous and nitrogen-containing active sites. Due to the abundant active sites, CQN anodes demonstrate excellent electrochemical capacity and good capacity retention rate. The CQN material has a structure similar to nitrogen-doped graphene and exhibits outstanding rate performance.
JOURNAL OF ENERGY STORAGE
(2023)
Article
Chemistry, Multidisciplinary
Hongmei Jiang, Haicheng Shen, Sha Zhu, Binbin Wang, Yujie Yang, Zhibin Nong, Min Yi, Shiyun Tang, Qing-Wen Gui
Summary: A novel and inexpensive double thiolation reagent has been reported for sulfurizing a broad range of imidazo[1,2-alpha]pyridines under mild conditions. Diethylaminosulfur trifluoride, a common nucleophilic fluorinating reagent, was utilized as the novel thiolation reagent in this study.
Article
Polymer Science
Bryton R. R. Varju, Dwight S. S. Seferos
Summary: This study reports the synthesis of pi-conjugated polymers with a degradable 1,2,4-oxadiazole linker using direct heteroaryl polymerization (DHAP). The 1,2,4-oxadiazole linker is stable under acidic, basic, and thermal conditions. The degradation of a small molecule model is achieved through reduction and acid hydrolysis. Phosphine-free and branching-suppressing DHAP conditions are employed for polymerization. DFT calculations are conducted to determine the affinity of the monomers for beta-branching defects. The synthesized polymers exhibit photoluminescence and high quantum yields of up to 0.40. Partial degradation of a representative polymer is observed under the same degradation conditions as the small molecule model.
Article
Chemistry, Physical
Pan-Pan Dai, Jun Han, Yi-Zhou Zhu, Yi-Qiao Yan, Jian-Yu Zheng
Summary: Dyes based on indeno[1,2-b]indole-spirofluorene (IISF) donor were synthesized and applied in dye-sensitized solar cells, showing different photovoltaic performance due to the different structures. The use of auxiliary diphenylamine donor and IISF donor had significant effects on the photovoltaic properties, with cocktail co-sensitizations promoting the power conversion efficiency.
JOURNAL OF POWER SOURCES
(2021)
Article
Chemistry, Multidisciplinary
Shuo Feng, Mochun Zhang, Yanxia Ma, Xue Ding, Tianran Yan, Yunling Wu, Wei Huang, Liang Zhang, Hualin Ye, Yujin Ji, Youyong Li, Yanguang Li
Summary: There is a growing interest in pi-d conjugated coordination polymers (CCPs) for energy storage due to their ability to facilitate rapid charge transfer. However, most reported CCPs for energy storage are based on 1D or 2D structures, and there are few 3D CCPs due to the challenge of constructing nonplanar coordination geometries. In this study, a triphenylene-catecholate-based 3D CCP (Mn-HHTP) was successfully synthesized and exhibited exceptional cycle life for multivalent Mg2+ ion storage, surpassing organic and inorganic electrode materials. Experimental and theoretical findings suggest that the semiquinone radicals at the HHTP ligands play a crucial role in storing Mg2+ ions. This research opens up new possibilities for designing 3D CCPs for long-life rechargeable magnesium-ion batteries.
ADVANCED MATERIALS
(2023)
Article
Biochemistry & Molecular Biology
Timofey N. Chmovzh, Timofey A. Kudryashev, Daria A. Alekhina, Oleg A. Rakitin
Summary: This study investigated the palladium-catalyzed direct (het)arylation reactions of electron-withdrawing tricyclic benzo[1,2-d:4,5-d']bis([1,2,3]thiadiazole) and its 4,8-dibromo derivative. Selective formation of mono- and bis-aryl derivatives was achieved under specific conditions. The direct C-H arylation of benzo[1,2-d:4,5-d']bis([1,2,3]thiadiazole) with bromo(iodo)arenes and -thiophenes in the presence of palladium acetate and di-tert-butyl(methyl)phosphonium tetrafluoroborate salt proved to be a powerful tool for selective formation of 4-mono- and 4,8-di(het)arylated benzo-bis-thiadiazoles. Oxidative double C-H hetarylation of benzo[1,2-d:4,5-d']bis([1,2,3]thiadiazole) with thiophenes in the presence of Pd(OAc)(2) and silver (I) oxide in DMSO successfully prepared bis-thienylbenzo-bis-thiadiazoles with moderate yields.
Review
Multidisciplinary Sciences
Dan Li, Jinlong Yang, Longjiu Cheng
Summary: Aromaticity is a crucial concept in chemistry, but there is currently no unified understanding for systems with conjugated sp(2) carbon. In this study, a superatomic-molecule theory is proposed to establish a generalized electron rule for various conjugated hydrocarbons, fullerenes, and 2D periodic materials. The theory considers polycyclic conjugated hydrocarbons and C-60 as superatomic molecules composed of bonded superatoms, leading to local aromaticity. Electron localization in superatomic molecules resembles classical valence bond theory. The proposed theory also predicts two 2D superatomic crystals with significant band gaps, despite the presence of conjugated and delocalized pi electrons. It provides a generalized chemical insight into local aromaticity and can be evaluated using superatomic Lewis structures. The theory serves as a unified language for aromaticity in diverse p-conjugated systems.
NATIONAL SCIENCE REVIEW
(2023)
Article
Chemistry, Multidisciplinary
Cristina Martin-Fuentes, Jose Urgel, Shayan Edalatmanesh, Eider Rodriguez-Sanchez, Jose Santos, Pingo Mutombo, Kalyan Biswas, Koen Lauwaet, Jose M. Gallego, Rodolfo Miranda, Pavel Jelinek, Nazario Martin, David Ecija
Summary: Among a variety of polycyclic structures emerging in recent years, indenofluorenes stand out as a unique class of compounds with potential in organic electronic systems. This study demonstrates the successful fabrication of pi-conjugated polymers of indeno[1,2-b]fluorene linked via cumulene-like connections on metallic surfaces under ultra-high vacuum conditions. The structure and electronic properties of these polymers have been characterized using advanced microscopy techniques and computational investigations.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Samuel Hruby, Jan Ulc, Ivana Cisarova, Martin Kotora
Summary: The scope of Rh-catalyzed C-C bond cleavage/annulation of biphenylene with various aromatic nitriles was investigated. Further Rh- and Ir-catalyzed C-H bond activation/annulation sequence of the resulting 9-arylphenanthridines with alkynes led to the formation of cationic [4], [5], [6] helical quinolizinium salts. The helical arrangement of these compounds was confirmed by single-crystal X-ray analysis. Most of the prepared quinolizinium salts exhibited fluorescence emission with a maximum wavelength in the range of 525-623 nm and absolute quantum yields up to 25%.
Article
Chemistry, Multidisciplinary
Shuhei Akahori, Takahiro Sasamori, Hiroshi Shinokubo, Yoshihiro Miyake
Summary: The self-assembly behavior of tetraazatetrathia[8]circulenes is revealed to be driven by both enthalpy and entropy, due to the unique structure of the molecules containing sp(2)-hybridized nitrogen atoms.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Yusuke Oyamada, Kazuto Inaba, Takahiro Sasamori, Shuichi Nakamura
Summary: This study achieved high enantioselectivity in the reaction of imines by introducing a cyano group as an activating group. The density functional theory (DFT) calculation clarified the stereochemical outcome and importance of the N-cyano group in the reaction.
CHEMICAL COMMUNICATIONS
(2022)
Article
Biochemistry & Molecular Biology
Kazuhira Miwa, Shinobu Aoyagi, Takahiro Sasamori, Shogo Morisako, Hiroshi Ueno, Yutaka Matsuo, Hideki Yorimitsu
Summary: The reduction of fullerene (C-60) with sodium dispersion in the presence of an excess amount of dipropyl sulfate yields highly propylated fullerene, C-60(nC(3)H(7))(n) (max. n = 24), with C-60(nC(3)H(7))(20) being predominantly generated as indicated by mass spectrometry.
Article
Chemistry, Organic
Takuya Murai, Yongning Xing, Mayu Kurokawa, Toshifumi Kuribayashi, Masanori Nikaido, Elghareeb E. Elboray, Shohei Hamada, Yusuke Kobayashi, Takahiro Sasamori, Takeo Kawabata, Takumi Furuta
Summary: A one-pot transformation method has been developed to convert biaryl dicarboxylic acids to (NH)-phenanthridinone derivatives using Curtius rearrangement and subsequent basic hydrolysis. This method is also applicable for preparing optically active amide-functionalized [7]helicene-like molecules. In addition, aza[5]helicene derivatives with a phosphate moiety were obtained as products of the Curtius rearrangement step when chalcogen atoms were present in the substrates. X-ray diffraction analysis revealed that chalcogen-bonding and pnictogen-bonding interactions may contribute to the stabilization of these compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Sudhir Lima, Atanu Banerjee, Gurunath Sahu, Sushree Aradhana Patra, Kausik Sahu, Takahiro Sasamori, Giuseppe Sciortino, Eugenio Garribba, Rupam Dinda
Summary: In this study, five new mononuclear mixed ligand oxidovanadium(IV) complexes were synthesized and characterized. These complexes contain tridentate O,N,O-donor aroylhydrazones as the main ligand and N,N-chelating 2,2'-bipyridine and 1,10-phenanthroline as the co-ligand. The interaction of these complexes with two proteins was studied, and their cytotoxicity against human cervical cancer and colon cancer cell lines was evaluated.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Sushree Aradhana Patra, Gurunath Sahu, Pratikshya Das Pattanayak, Takahiro Sasamori, Rupam Dinda
Summary: In this study, five fluorescent organotin(IV) complexes based on ONO donors were successfully synthesized and their photophysical properties were characterized. The results showed that these compounds were easily absorbed by cells and mainly internalized in mitochondria with negligible cytotoxicity at imaging concentration. Additionally, these complexes exhibited high photostability and could be used for long-term real-time tracking of cell organelles. Therefore, this low-toxic organotin-based fluorescent probe has potential applications in imaging mitochondria and tracking changes in their morphology within living cells.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Yusuke Oyamada, Shintaro Yamasaki, Mika Tsuzuki, Takumi Kitagawa, Masaru Kondo, Takahiro Sasamori, Shuichi Nakamura
Summary: The catalytic enantioselective allenylation of ketimines derived from isatins is reported. High regio- and enantioselective products were obtained using a bis(imidazoline)-palladium catalyst. The obtained products were further converted into various chiral amines. The stereoselectivity origin was revealed by DFT calculations of the transition state.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Narumi Itoh, Koh Sugamata, Shogo Morisako, Shinobu Aoyagi, Hideki Yorimitstu, Takahiro Sasamori
Summary: A stable dibenzo-1,6,2,5-dioxadisilocine was synthesized and used as a difunctional electrophile for double-silylation reactions. Its molecular structure was characterized by spectroscopic means and single-crystal X-ray diffraction analysis. Unexpected silylated polycyclic compound was obtained through reductive coupling of phenanthrene via formal [3+3] dimerization reaction.
Article
Chemistry, Inorganic & Nuclear
Mridhul R. K. Ramachandran, Philipp C. Brehm, Gregor Schnakenburg, Takahiro Sasamori, Rene T. Boere, Rainer Streubel
Summary: Tricyclic 1,4-dihydro-1,4-phosphasilines 3a,b were synthesized from Si(NR2)(2)-bridged imidazole-2-thione compounds 2a,b. Based on the calculated Frontier Molecular Orbitals (FMOs) of 3b, a possible P-selective P-N bond cleavage reduction could be predicted, and a redox cycle was established using solutions of P-centred anionic derivative K[4b]. The cycle started with the oxidation of K[4b] to form the P-P coupled product 5b, which could be chemically reduced by KC8 to regenerate K[4b].
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Medicinal
Takuya Murai, Shohei Hamada, Yusuke Kobayashi, Takahiro Sasamori, Takumi Furuta
Summary: The preparation, optical resolution, and structural investigations of a series of axially chiral biaryl dicarboxylic acids bearing oxygen, sulfur, and selenium atoms were conducted. The study revealed that the conformational control of these compounds can be achieved through chalcogen bonding interactions and tetrel bonding interactions. The physical and chiroptical properties of these biaryl dicarboxylic acids were also explored.
CHEMICAL & PHARMACEUTICAL BULLETIN
(2022)
Article
Chemistry, Inorganic & Nuclear
Marika Nakamura, Risa Hyakutake, Shogo Morisako, Takahiro Sasamori, Yoshiyuki Mizuhata, Norihiro Tokitoh, Kouichi Nakashima, Hiroki Fukumoto, Tomohiro Agou
Summary: This study successfully synthesized persistent radical complexes with multi-step electron transfer and long-wavelength absorption characteristics. These complexes exhibited reversible oxidation processes and showed potential as near-infrared active functional dyes.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Tomohiro Sugahara, Daisuke Hashizume, Norihiro Tokitoh, Hiroshi Matsui, Ryohei Kishi, Masayoshi Nakano, Takahiro Sasamori
Summary: This study presents the experimental visualization of the valence-electron-density distribution in benzene and its kinetically stabilized heavier-element analogues, 1,2-disilabenzene and 1,2-digermabenzene. The analysis indicates that the 1,2-disilabenzene and 1,2-digermabenzene have lower aromaticity compared to benzene due to the presence of incompletely delocalized pi electrons on their cyclic conjugation systems.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Organic
Takumi Inoue, Shohei Hamada, Rina Nakamura, Yusuke Kobayashi, Takahiro Sasamori, Takumi Furuta
Summary: An optically active form of an amide-functionalized thia[7]helicene-like molecule was prepared through the cyclization of the corresponding axially chiral d-amino acid. X-Ray analysis revealed its twisted helical structure with clockwise helicity and a pairwise association through hydrogen-bonding interactions.
Article
Chemistry, Multidisciplinary
Takahiro Sasamori, Tomohiro Sugahara, Norihiro Tokitoh
Summary: The corresponding amidinatosupported bromogermylene was obtained via the insertion of the C=N moiety into the Ge-C(Tbb) a-bond. The formation mechanism of the amidinato-supported bromogermylene was revealed by DFT calculations. This type of insertion reaction towards a metal-carbon bond can be interpreted in analogy to the reactivity of transition-metal complexes.
MENDELEEV COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Takahiro Sasamori, Hiromu Ueno, Shogo Morisako
Summary: A bisferrocenylsilane-bridged bisphosphine, with bis(1'-dicyclohexylphosphino-1-ferrocenyl)dimethoxysilane acting as the bridge, was synthesized and its structure was characterized. Cyclic voltammetry and differential pulse voltammetry were used to study its redox behavior, and two-step oxidation processes were observed.