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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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Abstract

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 theoretically to explore their electronic structures, absorption, and emissions as well as the solvatochromism. 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 contribute 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 electron-withdrawing group on ligand L will induce remarkable solvatochromism.

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Authors and Affiliations

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, China

    Tao Liu, Xin Zhou, FuQuan Bai, JianPo Zhang, BaoHui Xia & HongXing Zhang

  2. College of Chemistry, Jilin University, Changchun, 130023, China

    BaoHui Xia

  3. Laboratory of Physical Chemistry, School of Chemistry and Materials Science, Heilongjiang University, Harbin, 150080, China

    QingJiang Pan

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  1. Tao Liu
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  2. Xin Zhou
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  3. FuQuan Bai
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Correspondence to HongXing Zhang.

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Supported by the National Natural Science Foundation of China (Grant Nos. 20573042, 20703015, and 20333050)

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Liu, T., Zhou, X., Bai, F. et al. Theoretical studies on Ru(fppz)2(CO)L (L = N-heterocyclic ligand): Electronic structure, absorption, phosphorescence, and solvatochromism. Sci. China Ser. B-Chem. 51, 1211–1220 (2008). https://doi.org/10.1007/s11426-008-0131-3

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  • DOI: https://doi.org/10.1007/s11426-008-0131-3

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