A hybrid material based on [Mo6Br14]2- inorganic cluster units and [BEDO-TTF]+ organic monocationic radicals:: Synthesis, structure and properties of (BEDO-TTF)2Mo6Br14(PhCN)4

The first charge transfer salt based on non- dimerized [BEDO-TTF](+) monocationic radical (BEDO-TTF = bis(ethylenedioxy)tetrathiafulvalene) associated with [Mo6Br14](2-) cluster anions has been synthesized by conventional electro-oxidation and characterized by single crystal X-ray diffraction, UV-VIS-NIR absorption and magnetic susceptibility measurements. (BEDO-TTF)(2)Mo6Br14(PhCN)(4) crystallizes in the monoclinic system, space group P2(1)/n, a = 10.414(4) angstrom, b = 21.711(7) angstrom, c = 15.958(5) angstrom, beta = 93.65(3)degrees, V = 3601(2) angstrom(3), Z = 2, R-1 = 0.0578, wR(2) = 0.0731. The structure of this hybrid compound is built up from a [BEDO-TTF]+ and PhCN (benzonitrile) organic framework in which are hosted the [Mo6Br14](2-) inorganic cluster units. It results in non- dimerized [BEDOTTF]+ cations that exhibit a paramagnetic behavior characteristic of one unpaired electron. (c) 2006 Elsevier Inc. All rights reserved.