A Twin-TCNQ-Type Acceptor. Synthesis of 11,11,12,12,13,13,14,14-Octacyano-1,4:5,8-anthradiquinotetramethane and Structures of the Tetraethylammonium Salts of Its Mono- and Dianion

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公開日
1988-01-01
権利情報
  • https://academic.oup.com/pages/standard-publication-reuse-rights
DOI
  • 10.1246/bcsj.61.261
  • 10.1002/chin.198820130
公開者
Oxford University Press (OUP)

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<jats:title>Abstract</jats:title> <jats:p>The title compound (OCNAQ) was synthesized. Treatment of 1,2,3,4,5,6,7,8-octahydroanthracene with N-bromosuccinimide (NBS) under irradiation using a 100-W light bulb in refluxing CCl4 followed by dicyanomethylation with excess of NaCH(CN)2 in Me2SO gave an isomeric mixture of 1,4,5,8-tetrakis(dicyanomethyl) derivatives. The mixture was subjected by repetition of the successive bromination-dehydrobromination procedure giving OCNAQ in 20% overall yield. The cyclic voltammogram of OCNAQ exhibits four redox waves (E1⁄21 0.26, E1⁄22 0.05, E1⁄23 −0.44, and E1⁄24 −0.53 V vs. SCE in MeCN), indicating that OCNAQ is a stronger acceptor than tetracyanoquinodimethane (TCNQ, E1⁄21 0.17 V vs. SCE). Both 1:1 and 2:1 salts, (Et4N)(OCNAQ) and (Et4N)2(OCNAQ), were obtained from reactions of Et4NI with potassium and lithium salts of OCNAQ, respectively. The X-ray crystal analyses of these salts indicate that the TCNQ moieties are boat-shaped bent to opposite directions. With the 1:1 salt, which behaves as a semiconductor (4×10−4Ω−1 cm−1 at room temperature, Ea 0.22 eV), the OCNAQ molecules are arrayed in the segregated stacking mode, while the 2:1 salt (10−4Ω−1 cm−1) has no columnar structure of the OCNAQ molecules.</jats:p>

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