2,5-Bis(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione

N-propylsulfanyl and isopropylsulfanyl substituted 2,5-di(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione derivatives with methoxycarbonyl groups were synthesized, and their redox and electronic properties and crystal structures were investigated. Solid-state absorption spectra showed that both derivatives absorb almost all visible light. Furthermore isopropylsulfanyl-substituted derivatives absorb near-infrared light and the absorption edge reaches around 1320 nm. The crystal structures show that both derivatives are stacked in one dimension to form a columnar structure, but the molecular arrangements of their columns were quite different from each other. The stacked n-propylsulfanyl derivatives kept their orientation of thiocarbonyl groups in the same direction and the one molecule of the isopropylsulfanyl derivatives were rotated in relation to each other by an angle of 56° about their longer molecular axis. The TD-DFT calculation of stacked molecules suggests that the molecular arrangement among the stacked molecules affects the maximum absorption in near-infrared region.

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Zigzag Arrangement of Bromo-substituted 2,5-Di(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione Derivatives and Their Physical Properties

Ueda

Kunimoto

Henmi

et al. 2013

Chemistry Letters

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Four bromine-substituted 2,5-di(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione derivatives, 1a, 1b, 1c, and 1d, were synthesized, and their physical properties were investigated. These compounds were obtained from the reaction of a corresponding zinc complex of 2-(1,3-dithiol-2-ylidene)-1,3-dithiole-4,5-bis(thiolate) derivatives and corresponding tetrafluoroborate salts of 1,3-dithiol-2-ylium derivatives. Recrystallization of 1a from carbon disulfide and n-hexane gave single crystals suitable for X-ray structure analysis. In the crystal, 1a molecules are one-dimensionally stacked and one molecule is rotated relative to the neighboring molecules by an angle of 92° about its longer molecular axis. On the (010) plane, the molecules were arranged in a zigzag manner along the a axis. This interesting feature is accomplished by intermolecular S···Br halogen bonds.

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2,5-Bis(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione

Cited by 4 publications

References 14 publications

Five-Membered Ring Systems

Five-Membered Ring Systems

Syntheses, Crystal Structures and Solid-State Absorption Spectra of n-Propylsulfanyl- and Isopropylsulfanyl-Substituted 2,5-Di(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione Derivatives with Methoxycarbonyl Groups

Zigzag Arrangement of Bromo-substituted 2,5-Di(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione Derivatives and Their Physical Properties

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