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The First Assembly of a Nest‐Shaped Heterothiometallic Cluster and a Polyoxometalate Anion − Synthesis, Characterization, and Strong Third‐Order Nonlinear Optical Response
Author(s) -
Zhang Chi,
Song Yinglin,
Kühn Fritz E.,
Xu Yan,
Xin Xinquan,
Fun Hoongkun,
Herrmann Wolfgang A.
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(20021)2002:1<55::aid-ejic55>3.0.co;2-u
Subject(s) - polyoxometalate , chemistry , cluster (spacecraft) , crystallography , ion , cationic polymerization , nonlinear optics , halogen , stereochemistry , laser , optics , organic chemistry , physics , computer science , programming language , catalysis , alkyl
Two heterothiometallic cluster compounds [MOS 3 Cu 3 (4‐pic) 6 ]·0.5[M 2 O 7 ] (M = Mo 1 , W 2 ) having a cationic cluster skeleton and a polyoxometalate cluster anion, as well as two other clusters [MOS 3 Cu 3 (4‐pic) 6 ]·[BF 4 ] (M = Mo 3 , W 4 ) have been synthesized for nonlinear optics studies. Single‐crystal X‐ray diffraction data show that cluster 1 adopts a very interesting arrangement with a cationic nest‐shaped cluster skeleton and a polyoxomolybdenum cluster anion. This is the first time that such a skeleton has been found for an Mo/S/Cu heterothiometallic cluster compound and it represents a distinct structural type as compared to the analogous nest‐shaped clusters seen with a neutral or an anionic skeleton. The nonlinear optical properties of these four clusters have been investigated with an 8 ns pulsed laser at 532 nm, and optical self‐focusing effects have been observed. Clusters 1 and 2 with the polyoxometalate cluster anion exhibit stronger third‐order nonlinear optical absorption than clusters 3 and 4 having only a pseudo‐halogen group as the anion, which can be attributed to skeletal differences. Clusters 1 and 2 also exhibit very large optical limiting effects toward the ns incident pulsed laser as compared with clusters 3 and 4 and other shaped clusters with the same skeleton factors studied previously. This demonstrates the influence of the cluster skeleton on the nonlinear optical performance.