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Photoluminescent Metal–Sulfur Clusters Derived from Tetrathiometalates: Metal‐to‐Metal Charge‐Transfer Excited States of d 0 –d 10 Heterobimetallic Sulfido Clusters with Bulky Phosphine Ligands
Author(s) -
Che ChiMing,
Xia BaoHui,
Huang JieSheng,
Chan ChiKeung,
Zhou ZhongYuan,
Cheung KungKai
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20010917)7:18<3998::aid-chem3998>3.0.co;2-h
Subject(s) - chemistry , excited state , metal , crystallography , phosphine , electron transfer , sulfur , photochemistry , atomic physics , catalysis , biochemistry , physics , organic chemistry
Reactions of MS 4 2− (M=Mo, W) with M′(PCy 3 )X (M′=Ag/Au, X=ClO 4 /Cl) and [Cu 2 (dcpm) 2 (MeCN) 2 ](ClO 4 ) 2 (dcpm=bis(dicyclohexylphosphino)methane) afforded heterometallic sulfido clusters [M′ 2 (PCy 3 ) 2 (MS 4 )] (M=Mo, M′=Au: 2 ; M=W, M′=Ag: 3 , Au: 4 ) and [Cu 4 (dcpm) 4 (MS 4 )](ClO 4 ) 2 (M=Mo: 5⋅ (ClO 4 ) 2 , W: 6⋅ (ClO 4 ) 2 ), all of which, except 4 , have been characterized by X‐ray structure determination. Clusters 5⋅ (ClO 4 ) 2 and 6⋅ (ClO 4 ) 2 feature unusual 16‐membered {Cu 4 P 8 C 4 } 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 {Cu 4 MS 4 } core. Low‐energy absorption bands are observed in their electronic spectra at ∼562 and 467 nm, respectively, assignable to MMCT transitions; quasireversible reduction waves are observed with E 1/2 =−1.43 ( 5 2+ ) and −1.78 V ( 6 2+ ) versus FeCp 2 0/+ ; and they are emissive either in the solid state or in solution. The emission of 6 2+ can be quenched by both electron acceptors, such as methylviologen, or electron donors, such as aromatic amines, with the excited state reduction potential E ( 6 2+ */ 6 + ) estimated to be ∼1.13 V versus a normal hydrogen electrode.