title: Spectroscopic and phosphorescent modulation in triphosphine-supported PtAg2 heterotrinuclear alkynyl complexes.
abstract: A series of highly phosphorescent PtAg2 heterotrinuclear alkynyl complexes with bis(diphenylphosphinomethyl)phenylphosphine (dpmp) were prepared and characterized structurally. The solution phosphorescence with various emitting colors is systematically modulated by modifying substituents as well as π-conjugated systems in aromatic acetylides. The crystals, powders, or films exhibit reversible stimuli-responsive phosphorescence changes upon exposure to vapor of MeCN, pyridine, DMF, etc., resulting from perturbation of d(8)-d(10) metallophilic interaction in the excited states as a consequence of the formation/disruption of Ag-solvent bonds. Both experimental and time-dependent density functional theory (TD-DFT) studies demonstrate that d(8)-d(10) metallophilic interaction exerts a crucial role on phosphorescent characteristics due to the PtAg2 cluster-based (3)[d → p] state. This study affords a paradigm for phosphorescence modulation in d(8)-d(10) heteronuclear complexes.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
authors.forename: Li-Yi
authors.initials: LY
authors.lastname: Zhang
authors.forename: Liang-Jin
authors.initials: LJ
authors.lastname: Xu
authors.forename: Xu
authors.initials: X
authors.lastname: Zhang
authors.forename: Jin-Yun
authors.initials: JY
authors.lastname: Wang
authors.forename: Jia
authors.initials: J
authors.lastname: Li
authors.forename: Zhong-Ning
authors.initials: ZN
authors.lastname: Chen
mesh_terms: D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry*; D049408:Luminescent Agents / Q000138:chemical synthesis / Q000737:chemistry*; D008163:Luminescent Measurements; D008958:Models, Molecular; D010720:Phosphines / Q000138:chemical synthesis / Q000737:chemistry*; D017671:Platinum Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012834:Silver / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000480:Alkynes; D049408:Luminescent Agents; D010720:Phosphines; D017671:Platinum Compounds; D012834:Silver