In the present study,2,6-bis(diphenylphosphino)pyridine((Ph_(2)P)_(2)py)-supported cis-and trans-Pt_(2)Ag_(2)alkynyl complexes were prepared and characterized by X-ray crystallography.Although the cis-Pt_(2)Ag_(2)comp...In the present study,2,6-bis(diphenylphosphino)pyridine((Ph_(2)P)_(2)py)-supported cis-and trans-Pt_(2)Ag_(2)alkynyl complexes were prepared and characterized by X-ray crystallography.Although the cis-Pt_(2)Ag_(2)complexes are slightly emissive at ambient conditions,the trans-Pt_(2)Ag_(2)complexes exhibit moderate photoluminescence in dichloromethane and have strong emission in the solid state,originating from aromatic acetylide to(Ph_(2)P)_(2)py ligand-to-ligand charge transfer(^(3)LLCT)and Pt_(2)Ag_(2)cluster metal-centered(^(3)MC)triplet states.Remarkably,the trans-Pt_(2)Ag_(2)complex[Pt_(2)Ag_(2){(Ph_(2)P)_(2)py}_(2)(CuCC_(6)H_(5))_(4)](SO_(3)CF_(3))_(2)exhibit remarkable luminescent vapochromism with emission red-shifts of 100 nm in response to MeCN vapor,arising from intramolecular structural conversion from staggered to parallel arrangements of two face-to-face Pt(CuCC_(6)H_(5))_(2)moieties,which results in the alteration of the excited-state energy in the solid state as supported by TD-DFT studies.展开更多
基金National Natural Science Foundation of China(Grants 92061202,21531008 and 21801242)Fujian Science and Technology Project(Grant 2020L3022)Strategic Priority Research Program of Chinese Academy of Sciences(Grant XDB20000000)。
文摘In the present study,2,6-bis(diphenylphosphino)pyridine((Ph_(2)P)_(2)py)-supported cis-and trans-Pt_(2)Ag_(2)alkynyl complexes were prepared and characterized by X-ray crystallography.Although the cis-Pt_(2)Ag_(2)complexes are slightly emissive at ambient conditions,the trans-Pt_(2)Ag_(2)complexes exhibit moderate photoluminescence in dichloromethane and have strong emission in the solid state,originating from aromatic acetylide to(Ph_(2)P)_(2)py ligand-to-ligand charge transfer(^(3)LLCT)and Pt_(2)Ag_(2)cluster metal-centered(^(3)MC)triplet states.Remarkably,the trans-Pt_(2)Ag_(2)complex[Pt_(2)Ag_(2){(Ph_(2)P)_(2)py}_(2)(CuCC_(6)H_(5))_(4)](SO_(3)CF_(3))_(2)exhibit remarkable luminescent vapochromism with emission red-shifts of 100 nm in response to MeCN vapor,arising from intramolecular structural conversion from staggered to parallel arrangements of two face-to-face Pt(CuCC_(6)H_(5))_(2)moieties,which results in the alteration of the excited-state energy in the solid state as supported by TD-DFT studies.
