含双苯基膦或三苯基膦配体的手性铂（II）配合物中增强的圆偏振发光活性

Enhanced Circularly Polarized Luminescence Activity in Chiral Platinum(II) Complexes With Bis- or Triphenylphosphine Ligands.

作者信息

Yang Qian-Ying, Zhang Hua-Hong, Han Xue-Ling, Weng Shi-Dao, Chen Yuan, Wu Jia-Li, Han Li-Zhi, Zhang Xiao-Peng, Shi Zai-Feng

机构信息

Key Laboratory of Water Pollution Treatment & Resource Reuse of Hainan Province, College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou, China.

出版信息

Front Chem. 2020 Apr 24;8:303. doi: 10.3389/fchem.2020.00303. eCollection 2020.

Distinct circularly polarized luminescence (CPL) activity was observed in chiral (CNN)Pt(II) [(CNN) = 4,5-pinene-6'-phenyl-2,2'-bipyridine] complexes with bis- or triphenylphosphine ligands. Compared to the pseudo-square-planar geometry of chiral (CNN)Pt(II) complexes with chloride, phenylacetylene (PPV) and 2,6-dimethylphenyl isocyanide (Dmpi) ligands, the coordination configuration around the Pt(II) nucleus of chiral (CNN)Pt(II) complexes with bulk phosphine ligands is far more distorted. The geometry is straightforwardly confirmed by X-ray crystallography. The phosphines' participation enhanced the CPL signal of Pt(II) complexes profoundly, with the dissymmetry factor ( ) up to 10. The distorted structures and enhanced chiroptical signals were further confirmed by time-dependent density functional theory (TD-DFT) calculations.

在手性（CNN）Pt（II）[（CNN）= 4,5-蒎烯-6'-苯基-2,2'-联吡啶]与双苯基膦或三苯基膦配体形成的配合物中观察到了独特的圆偏振发光（CPL）活性。与具有氯、苯乙炔（PPV）和2,6-二甲基苯基异腈（Dmpi）配体的手性（CNN）Pt（II）配合物的准正方形平面几何结构相比，具有大量膦配体的手性（CNN）Pt（II）配合物中Pt（II）核周围的配位构型扭曲程度要大得多。该几何结构通过X射线晶体学得到了直接证实。膦的参与显著增强了Pt（II）配合物的CPL信号，不对称因子（）高达10。通过含时密度泛函理论（TD-DFT）计算进一步证实了扭曲结构和增强的手性光学信号。