Photochromic Isomerization of a Dinuclear Molybdenum Complex with Ethylene-1,2-Dithiolate and Disulfur Ligands: X-ray Structures of the Two Isomers

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• 作者：Takashi Shibahara ; Masanobu Tsuboi ; Shinsuke Nakaoka ; and Yasuhiro Ide
• 刊名：Inorganic Chemistry
• 出版年：2003
• 出版时间：February 24, 2003
• 年：2003
• 卷：42
• 期：4
• 页码：935 - 937
• 全文大小：76K
• 年卷期：v.42,no.4(February 24, 2003)
• ISSN：1520-510X

文摘

A photochromic complex with disulfur and dimethyl-ethylene-1,2-dithiolate ligands, [Mo₂(-S₂)(-S₂C₂Me₂)₂(S₂C₂Me₂)₂] (3), wassynthesized and characterized. Photoirradiation of 3 with visiblelight resulted in the formation of the isomer (3'). The electronicspectrum of 3' has a new intense peak in the near infrared region,and in the dark, the spectrum returns to that of 3. X-ray structuralanalyses of 3·C₆H₆ and 3' revealed a large conformational changeof the bridging dithiolate ligands: the two ligands in 3' come veryclose to each other compared to those in 3·C₆H₆. Crystal data:3·C₆H₆, monoclinic, space group C2/c, a = 15.193(4) Å, b =14.287(3) Å, c = 14.685(4) Å, = 105.30(1), V = 3074(1) ų,Z = 4; 3', monoclinic, space group C2/c, a = 21.5400(8) Å, b =9.5232(5) Å, c = 13.9828(2) Å, = 118.924(1), V = 2510.5(2)ų, Z = 4. ¹H NMR spectra of 3 (3.06, 3.05, 1.66, and 1.31 ppm)and 3' (2.90, 2.75, 2.14, and 1.97 ppm) are also reported: eachspectrum has four signals due to methyl groups, which accordswell with the fact that each of the molecules, 3·C₆H₆ and 3', hasa crystallographic 2-fold axis.