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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Structural, photophysical, and nonlinear absorption properties of trans-Di-arylalkynyl platinum(II) complexes with phenyl and thiophenyl groups
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Structural, photophysical, and nonlinear absorption properties of trans-Di-arylalkynyl platinum(II) complexes with phenyl and thiophenyl groups

机译：具有苯基和硫代苯基的反式-二-芳基炔基铂（II）配合物的结构，光物理和非线性吸收特性

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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.
机译：配体中有硫苯基和苯基的两个Pt（II）配合物的光功率限制和发光特性，反式-Pt（P（n-Bu）（3））（2）（CCAr）（2），其中Ar = C4H2SCC已研究了-p-C6H4-n-C5H11（1）和p-C6H4CCC4H3S（2）。发现荧光寿命在亚纳秒级，并且量子产率低，这与从激发单重态到三重态流形的快速系统间穿越相一致。 1和2的磷光寿命短于在配体中具有两个苯基的Pt（II）配合物。为了阐明基态的C-Pt键性质，直接键合到Pt的碳的C-13 NMR化学位移，耦合常数（1）J（PtC），（2）J（PtC）和对于1、2和其他三个反式二芳基炔基Pt（II）配合物，获得了（1）J（PtP）和IR nu（CC）波数。 1和2的X射线衍射数据以及密度泛函理论计算的1，2和反式Pt（P（n-Bu）（3））（2）（CC-p-C6H4CCC6H5）（2）模型的几何形状（3）表明1优选以不同于2和3的构象存在。光物理，NMR和IR数据的变化可以通过从Pt到炔基配体的几何形状和π-反向键的差异而合理化。

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