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Synthesis, structure and optical limiting properties of organoruthenium-chalcogenide clusters
Authors:Mark G Humphrey  Brian W Skelton  Allan H White  Brian F Yates
Institution:a Department of Chemistry, Australian National University, Canberra, ACT, 0200, Australia
b School of Chemistry, University of Tasmania, Private Bag 75, Hobart, TAS, 7001, Australia
c Laser Physics Centre, Research School of Physical Sciences and Engineering, Australian National University, Canberra, ACT, 0200, Australia
d Chemistry M313, University of Western Australia, Crawley, WA 6009, Australia
Abstract:Treatment of Ru3(CO)12 with Ph3PS affords the compounds Ru33-S)2(CO)9 − n(PPh3)n] (n = 1 (1a), 2 (2a)) and Ru33-S)(μ3-CO)(CO)7(PPh3)2] (3a) as the major products. Single crystal X-ray diffraction studies of Ru33-S)2(CO)8(PPh3)] and Ru33-S)(μ3-CO)(CO)7(PPh3)2] show these two classes of compounds to contain square pyramidal Ru3S2 and trigonal pyramidal Ru3S metal cores, respectively, with the latter being isostructural to the analogous selenide cluster compound. The clusters Ru33-E)2(CO)9 − n(PPh3)n] (E = S, n = 1; E = Se, n = 2) readily undergo ligand displacement reactions with PPh3 to afford the compounds Ru33-E)2(CO)6(PPh3)3] (E = S, 5a; E = Se 5b). The mixed chalcogenide cluster, Ru33-S)(μ3-Se)(CO)7(PPh3)2] (6), was prepared from the reaction of Ru33-S)(μ3-CO)(CO)7(PPh3)2] and SePPh3. The optical limiting properties of the complexes 1a,b, 2a,b, 5a,b have been measured by the Z-scan technique employing 40 ns pulses at 523 nm; power limiting was observed for all clusters under our experimental conditions.
Keywords:Chalcogenide  Ruthenium  Cluster  X-ray structure  Optical power limiting
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