Theoretical studies upon the electronic structures and spectroscopic properties for a series of luminescent terpyridyl platinum(II) phenylacetylide complexes |
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Authors: | Xin Zhou Qing-Jiang Pan Tao Liu Ming-Xia Li Hong-Xing Zhang |
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Affiliation: | aState Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China;bSchool of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China |
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Abstract: | A comprehensive calculations were carried out to get a deep insight into the ground- and excited-state electronic structures and the spectroscopic properties for a series of [Pt(4-X–trpy)CCC6H4R]+ complexes (trpy = 2,2′,6′,2″-terpyridine; X = H, R = NO2 (1), Cl (2), C6H5 (3) and CH3 (4); R = Cl, X = CH3 (5) and C6H5 (6)). MP2 (second-order Møller–Plesset perturbation) and CIS (single-excitation configuration interaction) methods were employed to optimize the structures of 1–6 in the ground and excited states, respectively. The investigation showed that substituted phenylacetylide and trpy ligands only give rise to a small variation in geometrical structures but lead to a sizable difference in the electronic structures for 1–6 in the ground and excited states. The introduction of electron-rich groups into the phenylacetylide and/or terpyridyl ligands produces two different low-lying absorptions for 1 and 2–6, i.e., Pt(5d) → π*(trpy) metal-to-ligand charge transfer (MLCT) mixed with π → π*(CCPh) intraligand charge transfer (ILCT) for 1 and Pt(5d)/π(CCPh) → π*(trpy) charge transfer (MLCT and LLCT) for 2–6. Remarkable electronic resonance on the whole Pt–CCPh–NO2 moiety for 1 may be responsible for the difference. Solvatochromism calculation revealed that only LLCT/MLCT transitions showed the solvent dependence, consistent with the experimental observations. |
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Keywords: | Excited state Luminescence Pt complexes |
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