Solvent-Induced Aggregation through Metal···Metal/π···π Interactions: Large Solvatochromism of Luminescent Organoplatinum(II) Terpyridyl Complexes

A dramatic color change and tremendous emission enhancement have been “switched on” upon increasing diethyl ether ratio in acetonitrile or acetone solution of [Pt(tpy)(C⋮C−C⋮CH)]OTf, attributed to the formation of Pt···Pt and π−π interactions. Two crystal forms (dark-green and red) of [Pt(tpy)(C⋮C−C⋮CH)]OTf, together with [Pt(tBu3-tpy)(C⋮C−C⋮CH)]OTf, show different crystal-packing modes as revealed by X-ray crystallography.

在[Pt(tpy)(C≡C−C≡CH)]三氟甲磺酸盐（[Pt(tpy)(C⋮C−C⋮CH)]OTf）的乙腈或丙酮溶液中，随着乙醚占比提升，体系被“激活”出显著的颜色变化与极强的发射增强效应，该现象源于Pt···Pt与π−π相互作用的生成。经X射线晶体学（X-ray crystallography）表征可知，[Pt(tpy)(C≡C−C≡CH)]OTf的两种晶型（深绿色与红色）以及[Pt(tBu3-tpy)(C≡C−C≡CH)]OTf呈现出截然不同的晶体堆积模式。