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

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• 作者：Kaplan Kirakci ; Hidemasa Hosoda ; Sté ; phane Cordier ; Christiane Perrin ; Gunzi Saito
• 关键词：Molybdenum ; Octahedral cluster ; Electro-oxidation ; BEDO-TTF cation ; Crystal structure ; X-ray diffraction ; UV– ; VIS– ; NIR spectroscopy ; Magnetism
• 刊名：Journal of Solid State Chemistry
• 出版年：2006
• 期刊代码：130_00224596
• 类别：ch
• 出版时间：December 2006
• 卷：179
• 期：12
• 页码：3628-3635
• 文件大小：529 K

摘要

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)₂Mo₆Br₁₄(PhCN)₄ crystallizes in the monoclinic system, space group P2₁/n, a=10.414(4) Å, b=21.711(7) Å, c=15.958(5) Å, β=93.65(3)°, V=3601(2) ų, me="mml2">method=retrieve&_udi=B6WM2-4KV2YK7-1&_mathId=mml2&_user=10&_cdi=6922&_rdoc=7&_acct=C000050221&_version=1&_userid=10&md5=60cc5a59e17ab8c16cc579a4da133609" title="Click to view the MathML source">Z=2, me="mml3">method=retrieve&_udi=B6WM2-4KV2YK7-1&_mathId=mml3&_user=10&_cdi=6922&_rdoc=7&_acct=C000050221&_version=1&_userid=10&md5=36b971cd12d9b3ddf2e6d9a204319df5" title="Click to view the MathML source">R₁=0.0578, me="mml4">method=retrieve&_udi=B6WM2-4KV2YK7-1&_mathId=mml4&_user=10&_cdi=6922&_rdoc=7&_acct=C000050221&_version=1&_userid=10&md5=775866118334eeb7d8f731ebd013e7e2" title="Click to view the MathML source">wR₂=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 [BEDO-TTF]⁺ cations that exhibit a paramagnetic behavior characteristic of one unpaired electron.