Crystal Engineering, Electron Conduction, and Molecular Recognition and Reactivity by Chalcogen Bonds in Tetracyanoquinodimethanes Fused with [1,2,5]Chalcogenadiazoles
Crystal Engineering, Electron Conduction, and Molecular Recognition and Reactivity by Chalcogen Bonds in Tetracyanoquinodimethanes Fused with [1,2,5]Chalcogenadiazoles
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晶体工程、电子传导以及与[1,2,5]硫属二唑稠合的四氰基醌二甲烷中硫属键的分子识别和反应性
DOI：
10.1055/a-2072-2951
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发表时间：
2023
期刊：
影响因子：
2
通讯作者：
Suzuki Takanori
中科院分区：
文献类型：
--
作者：
Shimajiri Takuya;Jacquot de Rouville Henri-Pierre;Heitz Val?rie;Akutagawa Tomoyuki;Fukushima Takanori;Ishigaki Yusuke;Suzuki Takanori
对一系列四氰喹啉二甲烷（TCNQs）与[1,2,5]硫代二唑环融合的研究表明，通过E•••N≡C （E = S或Se）接触的硫键（ChBs）是决定其晶体结构的决定性因素，在横向方向上形成一维或二维网络。对于单电子还原生成的阴离子自由基盐，由于涉及ChBs的分子间电子相互作用，电子在网络方向上发生传导。基于晶体工程中可靠的合成E••••N≡C，分子识别发生了，因此固态分子配合物通过电荷转移型笼形物在其异构体中选择性地与某些供体（如二甲苯）形成。包合物的包合腔可能为固相光致电子转移提供了反应环境。过度拥挤的乙烯表现出热/机械变色的多重构象的容纳是ChBs通过E•••N≡C触点可以实现的新功能的另一个例子。因此，这些具有形成ChBs能力的硫代二唑- tcnq是开发新型固态功能的有前景的材料介绍2双[1,2,5]噻二唑-TCNQ (BTDA)2.1 BTDA及其Se类似物晶体结构中的硫键2.2由btda组成的有机导体中硫键的电子效应2.3 btda分子配合物中硫键的分子识别2.4 btda分子配合物的单晶态光反应2.5由BTDA亚结构组成的过饱和乙烯3 TCNQ类似物与[1,2,5]硫代二唑融合3.1二硫代二唑- tcnnqs的晶体结构：E•••N≡C -氢•••N与弱C -氢•••N≡C -氢键3.3 TCNNQ衍生物中氯键的分子识别4展望
Studies on a series of tetracyanoquinodimethanes (TCNQs) fused with [1,2,5]chalcogenadiazole rings reveals that chalcogen bonds (ChBs), through E•••N≡C (E = S or Se) contacts, are a decisive factor in determining their crystal structures, with the formation of one- or two-dimensional networks in a lateral direction. For anion-radical salts generated by one-electron reduction, electron conduction occurs in the direction of the network due to intermolecular electronic interactions involving ChBs. Based on the reliable synthon E•••N≡C for crystal engineering, molecular recognition occurs so that solid-state molecular complexes are selectively formed with certain donors, such as xylenes, among their isomers by charge-transfer-type clathrate formation. The inclusion cavity of the clathrate might provide a reaction environment for photoinduced electron transfer in the solid state. The accommodation of multiple conformers of overcrowded ethylene exhibiting thermo/mechanochromism is another example of a novel function that can be realized by ChBs through E•••N≡C contacts. Therefore, these chalcogenadiazolo-TCNQs endowed with the ability to form ChBs are promising materials for the development of novel solid-state functions.1 Introduction2 Bis[1,2,5]thiadiazolo-TCNQ (BTDA)2.1 Chalcogen Bonds in Crystal Structures of BTDA and its Se Analogues2.2 Electronic Effects of Chalcogen Bonds in Organic Conductors Consisting of BTDA2.3 Molecular Recognition by Chalcogen Bonds in Molecular Complexes of BTDA2.4 Single-Crystalline-State Photoreactions of Molecular Complexes of BTDA2.5 Overcrowded Ethylene Composed of a BTDA Substructure3 TCNQ Analogues Fused with a [1,2,5]Chalcogenadiazole3.1 Crystal Structures of Chalcogenadiazolo-TCNQs3.2 Crystal Structures of Chalcogenadiazolo-TCNNQs: An E•••N≡C Chalcogen Bond versus a Weak C–H•••N≡C Hydrogen Bond3.3 Molecular Recognition by Chalcogen Bonds in TCNNQ Derivatives4 Outlook