Spectroscopic properties and crystal structures of luminescent linear tri- and tetra-nuclear gold(I) complexes with bis(diphenylphosphinomethyl)phenylphosphine ligand
- 1 January 1993
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 1,p. 189-194
- https://doi.org/10.1039/dt9930000189
Abstract
Reaction of [AuCl4]– with 2,2′-thiodiethanol in methanol generated AuIin situ, which reacted with bis(diphenylphosphinomethyl)phenylphospine (dpmp) and NaSCN to give [Au4(dpmp)2(SCN)2]2+ and [Au3(dpmp)2]3+. The crystal structures of [Au4(dpmp)2(SCN)2][SCN]Cl and [Au3(dpmp)2][SCN]3 have been determined: [Au3(dpmp)2][SCN]3, monoclinic, space group P21/n, a= 12.474(4), b= 25.575(4), c= 20.182(6)Å, β= 92.61(3)° and Z= 4; [Au4(dpmp)2(SCN)2][SCN]Cl, space group P(no. 2), a= 13.799(2), b= 14.061(2), c= 19.390(4)Å, α= 88.46(2), β= 75.41(1), γ= 74.58(1)° and Z= 2. They comprise nearly linear Au3 and Au4 chains with Au–Au–Au angles of 167.21(2)° for [Au3(dpmp)2][SCN]3, 160.0(1) and 167.2(1) for [Au4(dpmp)2][SCN]Cl. A weak AuI–AuI bonding interaction is anticipated in view of the intramolecular Au ⋯ Au separations. Both complexes show room-temperature photoluminescence. The red shift in the dσ*→ pσ transition energy from [Au2(dppm)2]2+[dppm = bis(diphenylphosphino)methane] to [Au3(dpmp)2]3+ and to [Au4(dpmp)2(SCN)2]2+ has been attributed to the bonding interactions between adjacent P2Au units. The photophysical properties of [Au3(dpmp)2][SCN]3 are discussed.Keywords
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