Systematic Change in Stacking Structure Induced by Alkyl Chains and Spectral Change Due to Hetero-Aggregation in [Ni(dmit)<sub>2</sub>]<sup>−</sup>Salts of Methylene Blue Analogues
作者:Yuji Soneta、Kazuo Miyamura
DOI:10.1246/bcsj.79.282
日期:2006.2
A series of [Ni(dmit)2]− (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato) salts of 3,7-bis(dialkylamino)phenothiazin-5-ium (alkyl = methyl (C1S), ethyl (C2S), propyl (C3S), and butyl (C4S)) together with those of 3,7-bis(diallylamino)phenothiazin-5-ium (AS) and 3,7-bis(diethylamino)phenoxazin-5-ium (C2O) have been prepared and analyzed by X-ray crystal structural analysis and diffuse reflectance spectra. All complex salts formed stacking columns containing cations and anions. In the crystal structure of (C1S)[Ni(dmit)2], both C1S cations and [Ni(dmit)2]− anions were found to form stacked dimers, and these dimers piled up alternately in columns. In the cases of (C2S)[Ni(dmit)2], (AS)[Ni(dmit)2], and (C2O)[Ni(dmit)2], cations and anions piled up alternately in the form of monomers. In the cases of (C3S)[Ni(dmit)2] and (C4S)[Ni(dmit)2], one anion was sandwiched between two cation dimers to form columns, and another anion layed between these columns. An absorption band appeared at 516–566 nm in the diffuse reflectance spectra, which originated from the absorption of blue cationic dyes, exhibited a large shift by the intermolecular interaction of cation–cation and cation–anion π-stacking. Compounds of (C1S)[Ni(dmit)2] and (C2O)[Ni(dmit)2] were found to behave as semiconductors, exhibiting room temperature conductivities of 3.8 × 10−6 and 4.5 × 10−7 S cm−1, respectively.
3,7-双(二烷基氨基)吩噻嗪-5-鎓(烷基=甲基( C1S)、乙基(C2S)、丙基(C3S)和丁基(C4S))以及3,7-双(二烯丙基氨基)吩噻嗪-5-鎓(AS)和3,7-双(二乙基氨基)吩恶嗪-的那些5-ium (C2O) 已制备并通过 X 射线晶体结构分析和漫反射光谱进行分析。所有复合盐形成含有阳离子和阴离子的堆积柱。在(C1S)[Ni(dmit)2]的晶体结构中,C1S阳离子和[Ni(dmit)2]−阴离子均形成堆叠二聚体,并且这些二聚体交替堆积成柱状。在(C2S)[Ni(dmit)2]、(AS)[Ni(dmit)2]和(C2O)[Ni(dmit)2]的情况下,阳离子和阴离子以单体的形式交替堆积。在(C3S)[Ni(dmit)2]和(C4S)[Ni(dmit)2]的情况下,一个阴离子夹在两个阳离子二聚体之间形成柱,另一个阴离子位于这些柱之间。漫反射光谱中516-566 nm处出现一个吸收带,该吸收带源自蓝色阳离子染料的吸收,由于阳离子-阳离子和阳离子-阴离子π堆积的分子间相互作用而表现出较大的位移。 (C1S)[Ni(dmit)2] 和 (C2O)[Ni(dmit)2] 化合物被发现具有半导体性质,表现出 3.8 × 10−6 和 4.5 × 10−7 S cm−1 的室温电导率, 分别。