Spectroscopic and Phosphorescent Modulation in Triphosphine-Supported PtAg2 Heterotrinuclear Alkynyl Complexes

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• 作者：Li-Yi Zhang ; Liang-Jin Xu ; Xu Zhang ; Jin-Yun Wang ; Jia Li ; Zhong-Ning Chen
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：May 6, 2013
• 年：2013
• 卷：52
• 期：9
• 页码：5167-5175
• 全文大小：505K
• 年卷期：v.52,no.9(May 6, 2013)
• ISSN：1520-510X

文摘

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 蟺-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 d⁸-d¹⁰ metallophilic interaction in the excited states as a consequence of the formation/disruption of Ag鈥搒olvent bonds. Both experimental and time-dependent density functional theory (TD-DFT) studies demonstrate that d⁸-d¹⁰ metallophilic interaction exerts a crucial role on phosphorescent characteristics due to the PtAg₂ cluster-based ³[d 鈫?p] state. This study affords a paradigm for phosphorescence modulation in d⁸鈥揹¹⁰ heteronuclear complexes.