Structural, Photophysical, And Nonlinear Absorption Properties Of Trans-Di-Arylalkynyl Platinum(Ii) Complexes With Phenyl And Thiophenyl Groups
JOURNAL OF PHYSICAL CHEMISTRY A(2007)
摘要
Optical power limiting and luminescence properties of two Pt(II) complexes with thiophenyl and phenyl groups in the ligands, trans-Pt(P(n-Bu)(3))(2)(CCAr)(2), where Ar = C4H2SCC-p-C6H4-n-C5H11 (1) and p-C6H4CCC4H3S (2), have been investigated. The fluorescence lifetimes were found to be on the sub-nanosecond time scale, and the quantum yields were low, in accord with fast intersystem crossing from the excited singlet to triplet manifold. The phosphorescence lifetimes of 1 and 2 were shorter than that of a Pt(II) complex having two phenyl groups in the ligands. In order to elucidate the C-Pt bonding nature in the ground state, the C-13 NMR chemical shift of the carbon directly bonded to Pt, the coupling constants (1)J(PtC), (2)J(PtC), and (1)J(PtP), and IR nu(CC) 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 models of 1, 2, and trans-Pt(P(n-Bu)(3))(2)(CC-p-C6H4CCC6H5)(2) (3) show that 1 preferably exists in a different conformation from that of 2 and 3. The variations in photophysical, NMR, and IR data can be rationalized by differences in geometry and pi-backbonding from Pt to the alkynyl ligand.
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关键词
nonlinear absorption properties,complexes,thiophenyl groups,photophysical,di-arylalkynyl
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