Structural, Photophysical, and Nonlinear Absorption Properties of trans-Di-arylalkynyl Platinum(II) Complexes with Phenyl and Thiophenyl Groups
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- 作者：Per Lind ; Dan Boströ ; m ; Marcus Carlsson ; Anders Eriksson ; Eirik Glimsdal ; Mikael Lindgren ; Bertil Eliasson
- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：March 8, 2007
- 年：2007
- 卷：111
- 期：9
- 页码：1598 - 1609
- 全文大小：329K
- 年卷期：v.111,no.9(March 8, 2007)
- ISSN：1520-5215
文摘
Optical power limiting and luminescence properties of two Pt(II) complexes with thiophenyl and phenylgroups in the ligands, trans-Pt(P(n-Bu)3)2(C
d1.gif">C-Ar)2, where Ar = -C4H2S-Cd1.gif">C-p-C6H4-n-C5H11 (1) and-p-C6H4-Cd1.gif">C-C4H3S (2), have been investigated. The fluorescence lifetimes were found to be on thesub-nanosecond time scale, and the quantum yields were low, in accord with fast intersystem crossing fromthe excited singlet to triplet manifold. The phosphorescence lifetimes of 1 and 2 were shorter than that of aPt(II) complex having two phenyl groups in the ligands. In order to elucidate the C-Pt bonding nature in theground state, the 13C NMR chemical shift of the carbon directly bonded to Pt, the coupling constants 1JPtC,2JPtC, and 1JPtP, and IR 
Cd1.gif">C wavenumbers were obtained for 1, 2, and three other trans-diarylalkynyl Pt(II)complexes. X-ray diffraction data of 1 and 2 and density functional theory calculated geometries of modelsof 1, 2, and trans-Pt(P(n-Bu)3)2(Cd1.gif">C-p-C6H4-Cd1.gif">C-C6H5)2 (3) show that 1 preferably exists in a differentconformation from that of 2 and 3. The variations in photophysical, NMR, and IR data can be rationalizedby differences in geometry and 
-backbonding from Pt to the alkynyl ligand.
d1.gif">C-Ar)2, where Ar = -C4H2S-Cd1.gif">C-p-C6H4-n-C5H11 (1) and-p-C6H4-Cd1.gif">C-C4H3S (2), have been investigated. The fluorescence lifetimes were found to be on thesub-nanosecond time scale, and the quantum yields were low, in accord with fast intersystem crossing fromthe excited singlet to triplet manifold. The phosphorescence lifetimes of 1 and 2 were shorter than that of aPt(II) complex having two phenyl groups in the ligands. In order to elucidate the C-Pt bonding nature in theground state, the 13C NMR chemical shift of the carbon directly bonded to Pt, the coupling constants 1JPtC,2JPtC, and 1JPtP, and IR Cd1.gif">C wavenumbers were obtained for 1, 2, and three other trans-diarylalkynyl Pt(II)complexes. X-ray diffraction data of 1 and 2 and density functional theory calculated geometries of modelsof 1, 2, and trans-Pt(P(n-Bu)3)2(Cd1.gif">C-p-C6H4-Cd1.gif">C-C6H5)2 (3) show that 1 preferably exists in a differentconformation from that of 2 and 3. The variations in photophysical, NMR, and IR data can be rationalizedby differences in geometry and -backbonding from Pt to the alkynyl ligand.