Photophysical Properties of Pt(II) Polypyridines with Five- versus Six-Membered Chelate Rings: Trade-Offs in Angle Strain
作者:Sean N. Natoli、Lauren M. Hight、Matthias Zeller、David R. McMillin
DOI:10.1021/acs.inorgchem.8b00636
日期:2018.6.4
lifetimes than [Pt(trpy)C2Ph]+. One reason is that the bond angle preferences of platinum and the inserted heteroatom induce the six-membered rings to deviate from planarity and adopt a boat-like conformation, impairing charge delocalization within the ligand. In addition, angle strain induces the donor atoms about platinum to assume a pseudotetrahedral arrangement, which offsets any benefit due to the increase
该报告描述了八种[Pt(NNN)X] +配合物的合成和表征,其中三齿NNN配体为(2,2'-bipyrid-6-yl)(pyrid-2-yl)硫化物(btp)或甲基(2,2'-联吡啶-6-基)(吡啶-2-基)胺(bmap),X为OMe,Cl,苯基乙炔基(C 2 Ph)或环己基乙炔基(C 2 Cy)。期望将杂原子插入2,2':6',2''-三联吡啶(trpy)的骨架中将扩大整体配体内咬合角,将ILCT特性引入激发态,并改善光物理性质。[ Pt(bmap)C 2 Ph ] +和[ Pt(btp)的晶体结构。)Cl ] +揭示原子插入trpy主链成功地将配体的咬合角扩大了8-10°。但是,对光物理的影响很小。实际上,在研究的八个系统中,只有[ Pt(bmap)C 2 Ph ] +和[ Pt(btp)C 2 Ph ] +络合物在流体溶液中显示出可观的发射,并且它们的发射寿命比[Pt(trpy) )C