Methylthio- and ethanediyldithio-substituted 1,6-dithiapyrenes and their charge-transfer complexes: new organic molecular metals

Journal Article · Wed Nov 11 00:00:00 EST 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00257a011· OSTI ID:7076534

Nakasuji, K; Sasaki, M; Kotani, T; Murata, I; Enoki, T; Imaeda, K; Inokuchi, H; Kawamoto, A; Tanaka, J

The synthesis and physical properties of 2,7-bis(methylthio)-1,6-diathiapyrene (MTDTPY) and 2,3:7,8-bis(ethanediyldithio)-1,6-dithiapyrene (ETDTPY) and their charge-transfer complexes are reported. MTDTPY was prepared from 1,6-dithiapyrene. ETDTPY was prepared from naphthalene-1,5-dithiol in four steps. These two new donors showed reversible two-stage redox behavior with potentials comparable to that of tetrathiafulvalene. MTDTPY produced two crystalline phases of 1:1 TCNQ complexes, the ..cap alpha..-form (monoclinic, P2/sub 1//c) and the ..beta..-form (triclinic, P anti 1), which consist of mixed stacks and uniform segregated stacks of donors and acceptors, respectively. The ..beta..-form contained short S...S contacts between adjacent donor columns (3.48 and 3.57 A). The single-crystal conductivity of the ..beta..-form was metallic (sigma/sub rt/ = 110 S cm/sup -1/, T/sub c/ = 110 K), while that of the ..cap alpha..-form was semiconductive (sigma/sub rt/ = 3.4 x 10/sup -6/ S cm/sup -1/). MTDTPY-chloranil crystallized in uniform segregated stacks of donors and acceptors (triclinic P anti 1). Relatively short interstack S...S contacts were also observed (3.60 and 3.67 A). The single-crystal conductivity was metallic (sigma/sub rt/ = 140 S cm/sup -1/, T/sub c/ = 240 K). MTDTPY-bromanil also showed metallic conductivity (sigma/sub rt/ = 230 S cm/sup -1/, T/sub c/ = 125 K). The long needle crystals of MTDTPY-I/sub 2.2/ and ETDTPY-I/sub 2.3/ showed semiconducting behavior with relatively high conductivities, 13 and 42 S cm/sup -1/, respectively.

• Research Organization: Osaka Univ. (Japan)
• OSTI ID: 7076534
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 109:23
• Country of Publication: United States
• Language: English

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400201* - Chemical & Physicochemical Properties
360603 - Materials- Properties