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theoretical study of the electronic structures and spectroscopic properties of [(4'-XC≡Ctrpy)PtCl]^+ (trpy=2,2':6',2"-terpyridine;X=H,Me and Ph)

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Science china chemistry 2009年第12期52卷 2226-2236页

作者： wang xin,bai fuquan,zhou xin,liu tao & zhang hongxing state key laboratory of theoretical and computational chemistry,institute of theoretical chemistry,jilin university,changchun 130023,china state key laboratory of theoretical and computational chemistry Institute of Theoretical Chemistry Jilin University Changchun China

The electronic structures and spectroscopic properties of [(4'-XC≡Ctrpy)PtCl]+(trpy = 2,2':6',2″-terpyridine; X = H (1),methyl (Me) (2),and phenyl (Ph) (3) were studied by the ab initio method. The structures at the ground and excited state were optimized at the B3LYP and CIS levels,respectively. The absorption and emission spectra in the dichloromethane solution were obtained by using the TD-DFT (B3LYP) method associated with the PCM model. The molecular orbital energy of the HOMOs of 1-3 with the d(Pt),p(Cl),π(trpy),and π(XC≡C) character is sensitive to the substituents on the acetylide ligand,but that of the trpy-based LUMOs with the π*(trpy) character varies slightly. The lowest lying emission at 503 nm for 1 is mainly attributed to the 3ILCT perturbed by the 3MLCT and 3LLCT transitions,but that at 535 nm for 2,and that at 558 nm for 3 are mainly attributed to the 3LLCT perturbed by the 3ILCT and 3MLCT transitions. The different electron-donating ability of H,Me,and Ph is responsible for the differences in emission character. Moreover,the calculation results show that the phosphorescent color can be turned by adjusting the substituents. Both the lowest energy absorption and emission of 1―3 are red-shifted in the order of 1<2<3,consistent with the electron-donating of H

关键词： platinum(Ⅱ) complexes TD-DFT absorption spectra charge transfer luminescence

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theoretical studies on Ru(fppz)_2(CO)L (L=N-heterocyclic ligand):Electronic structure,absorption,phosphorescence,and solvatochromism

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Science china chemistry 2008年第12期51卷 1211-1220页

作者： liu tao1, zhou xin1, bai fuquan1, zhang JianPo1, XIA BaoHui1,2, PAN QingJiang3 & zhang hongxing1 1 state key laboratory of theoretical and computational chemistry, institute of theoretical chemistry, jilin university, changchun 130023, china 2 College of chemistry, jilin university, changchun 130023, china 3 laboratory of Physical chemistry, School of chemistry and Materials Science, Heilongjiang university, Harbin 150080, china state key laboratory of theoretical and computational chemistry Institute of Theoretical Chemistry Jilin University Changchun China College of chemistry Jilin University Changchun China laboratory of Physical chemistry School of Chemistry and Materials Science Heilongjiang University Harbin China

A series of ruthenium(II) complexes Ru(fppz)2(CO)L [fppz = 3-trifluoromethyl-5(2-pyridyl)pyrazole; L = pyridine (1), 4-dimethylaminopyridine (2), 4-cyanopyridine (3)] were designed and investigated theo-retically to explore their electronic structures, absorption, and emissions as well as the solvatochrom-ism. The singlet ground state and triplet excited state geometries were fully optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ level, respectively. The HOMO of 1-3 is composed of dyz(Ru) atom and π(fppz). The LUMO of 1 and 2 is dominantly contributed by π*(fppz) orbital, but that of 3 is con-tributed by π*(L). Absorption and phosphorescence in vacuo, C6H12, and CH3CN media were calculated using the TD-DFT level of theory with the PCM model based on the optimized ground and excited state geometries, respectively. The lowest-lying absorption of 1 and 2 at 387 and 391 nm is attributed to {[dyz(Ru) + π(fppz)] → [π*(fppz)]} transition, but that of 3 at 479 nm is assigned to {[dyz(Ru) + π(fppz)] → [π*(L)]} transition. The phosphorescence of 1 and 2 at 436 and 438 nm originates from 3{[dyz(Ru) + π(fppz)] [π*(fppz)]} excited state, while that of 3 at 606 nm is from 3{[dyz(Ru) + π(fppz)] [π*(L)]} excited state. The calculation results showed that the absorption and emission transition character can be changed from MLCT/ILCT to MLCT/LLCT transition by altering the substituent on the L ligand. The phosphorescence of 1 and 2 does not have solvatochromism, but that of 3 at 606 nm (vacuo), 584 nm (C6H12), and 541 nm (CH3CN) is strongly dependent on the solvent polarity, so introducing elec-tron-withdrawing group on ligand L will induce remarkable solvatochromism.

关键词： ruthenium complex DFT phosphorescence solvatochromism

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