Synthesis, structure and absorption spectrum of a new charge transfer salt [Fe(C5H5)2]4H[GeMo12O40] · CH3CN · H2O

Author： Li Zhanfeng Cui Ruirui Xue Ganglin Hu Huaiming Fu Feng Wang Jiwu

ISSN： 0095-8972

Source： Journal of Coordination Chemistry, Vol.62, Iss.12, 2009-06, pp. : 1951-1958

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Abstract

A new charge-transfer (CT) salt based on Fe(C5H5)2 and Keggin-type anion [GeMo12O40]4-, [Fe(C5H5)2]4HGeMo12O40 · CH3CN · H2O, was electrochemically synthesized and its structure was determined by single-crystal X-ray diffraction. Triclinic, P1, M = 2668.07, a = 12.600(9) Å, b = 13.033(4) Å, c = 13.298(5) Å, α = 116.312(6)°, β = 101.244(9)°, γ = 92.919(9)°, V = 1896.4(16) Å3, Z = 1, R1 = 0.0673, wR2 = 0.1667(I > 2σ). [image omitted] moieties are stacked to form quadrangle channels with distances of [image omitted] and [image omitted] between the cyclopentadienyl rings of two adjacent ferrocene cations along the [0 1 1] direction that accommodate the polyanions, and each polyanion is surrounded by eight adjacent [Fe(C5H5)2]+ units with the nearest distance of framework oxygens of Keggin anions and carbon atoms of [Fe(C5H5)2]+ cations from 2.996 Å to 3.201 Å. The UV-Vis spectrum in concentrated solution indicates the presence of a new band at λmax = 620 nm, ascribed to CT transitions between the ferrocenyl donors and the Polyoxometalate acceptors. IR, EPR, and CV properties of the salts were also discussed.