Multiplex Proton-Transfer and Electron-Transfer Natures Based on the 2,2′-Bi-1H-imidazole System. II. Crystal Structures and Charge-Transfer Complex Formations
Multiplex Proton-Transfer and Electron-Transfer Natures Based on the 2,2′-Bi-1H-imidazole System. II. Crystal Structures and Charge-Transfer Complex Formations
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基于 2,2-Bi-1H-咪唑系统的多重质子转移和电子转移性质 II。
DOI：
10.1246/bcsj.69.2487
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发表时间：
1996
影响因子：
4
通讯作者：
Ken
中科院分区：
文献类型：
--
作者：
T. Akutagawa;G. Saito;M. Kusunoki;Ken
对2，2 ′-联-1H-咪唑（H2 BIM 0）的晶体结构和电荷转移（CT）配合物形成的研究表明，H2 BIM 0形成了一个涉及质子转移（PT）和电子转移（或电荷转移（CT））相互作用的新体系。新分离的2-（2- 1H-咪唑基）-1H-咪唑鎓（H3 BIM+）和2，2 ′-联-1H-咪唑鎓（H4 BIM 2+）的X射线晶体分析表明，它们在分子平面的沿着方向上形成了强氢键。用复分解法合成了H3 BIM+和H4 BIM 2+与7，7，8，8-四氰基醌二甲烷衍生物（TCNQs）的CT配合物，并测定了（H3 BIM+）2（TCNQ−）2（TCNQ 0）的晶体结构.在CT复合物形成过程中，[H3 BIM +]或[H4 BIM 2 +]的初始简单质子化状态变为不同的状态，例如[H4 BIM 2 +]x[H3 BIM +]1−x，[H3 BIM +]x[H2 BIM 0]1−x和H2 BIM 0。根据H_2BIM体系的质子化状态，CT络合物中TCNQ的形式电荷从完全不同到完全不同。
Studies of the crystal structures and formation of a charge-transfer (CT) complex proved that 2,2′-bi-1H-imidazole (H2BIM0) forms a new system concerned with the interplay of proton-transfer (PT) and electron-transfer (or charge-transfer (CT)) interactions. X-Ray crystal analyses of newly isolated species, 2-(2-1H-imidazolyl)-1H-imidazolium (H3BIM+) and 2,2′-bi-1H-imidazolium (H4BIM2+), revealed the formation of strong hydrogen bonds along the side-by-side direction of the molecular plane. CT complexes of H3BIM+ and H4BIM2+ with the 7,7,8,8-tetracyanoquinodimethane derivatives (TCNQs) were synthesized by a method metathesis, and the crystal structure of (H3BIM+)2(TCNQ−)2(TCNQ0) was determined. During CT complex formation, the initial simple protonated states of [H3BIM+] or [H4BIM2+] changed to different ones, for example, [H4BIM2+]x[H3BIM+]1−x, [H3BIM+]x[H2BIM0]1−x, and H2BIM0. According to the protonated states of the H2BIM system, the formal charge of the TCNQs in the CT complexes varies from completely...