Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Systematic Change in Stacking Structure Induced by Alkyl Chains and Spectral Change Due to Hetero-Aggregation in [Ni(dmit)2] Salts of Methylene Blue Analogues
Yuji SonetaKazuo Miyamura
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2006 Volume 79 Issue 2 Pages 282-287


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.

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© 2006 The Chemical Society of Japan
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