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Title: Photoluminescent metal-sulfur clusters derived from tetrathiometalates : metal-to-metal charge-transfer excited states of d0-d10 heterobimetallic sUlfido clusters with bulky phosphine ligands
Authors: Che, CM
Xia, BH
Huang, JS
Chan, CK
Zhou, ZY
Cheung, KK
Keywords: Cluster compounds
Structure elucidation
Issue Date: 2001
Publisher: Wiley-VCH
Source: Chemistry - a European journal, 2001, v. 7, no. 18, p. 3998-4006 How to cite?
Journal: Chemistry - a European journal 
Abstract: Reactions of MS4 2- (M = Mo, W) with M′(PCy3)X (M′ = Ag/Au, X = ClO4/Cl) and [Cu2(dcpm)2(MeCN)2]-(ClO4) 2 (dcpm = bis(dicyclohexylphosphino)methane) afforded heterometallic sulfido clusters [M′2(PCy3)2(MS4)] (M = Mo, M′ = Au: 2; M = W, M′ = Ag: 3, Au: 4) and [Cu4(dcpm)4(MS4)](ClO4)2 (M = Mo: 5·(ClO4)2, W: 6·(ClO4)2), all of which, except 4, have been characterized by X-ray structure determination. Clusters 5·(ClO4)2 and 6·(ClO4)2 feature unusual 16-membered {Cu4P8C4} metallamacrocycles formed on the respective tetrathiometalate anion templates and have unusually long Cu-S bonds and Cu-M distances for metal-sulfur clusters that contain a saddle-shaped {Cu4MS4} core. Low-energy absorption bands are observed in their electronic spectra at ∼562 and 467 nm, respectively, assignable to MMCT tran-sitions; quasireversible reduction waves are observed with E1/2 = -1.43 (52+) and -1.78 V (62+) versus FeCp2 0/+; and they are emissive either in the solid state or in solution. The emission of 62+ can be quenched by both electron acceptors, such as methylviologen, or electron donors, such as aromatic amines, with the excited state reduction potential E(62+*/6+) estimated to be ∼1.13 V versus a normal hydrogen electrode.
ISSN: 0947-6539
EISSN: 1521-3765
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