Journal
JOURNAL OF MOLECULAR STRUCTURE
Volume 1195, Issue -, Pages 620-631Publisher
ELSEVIER
DOI: 10.1016/j.molstruc.2019.06.005
Keywords
Ru mono-diimine complexes; Triplet excited state; Stokes shift; HOMO-LUMO energy gap; Trans influence; Density functional theory
Categories
Funding
- National Science Foundation [ACI-1548562, TG-CHE160010]
- National Institutes of Health Centers of Biomedical Research Excellence (CoBRE) Award [P20GM103546]
- National Science Foundation award (NSF) [MRI CHE-1337908]
- Imam Abdulrahman Bin Faisal University, Saudi Arabia
- University of Montana
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The ground (S-0) and excited triplet (T-1) electronic states and corresponding optical spectra of a series of cationic complexes [RuH(CO)L(PPh3)(2)](+) (L = 2,2'-bipyridyl) (Rubpy), 4,4'-dicarboxylic-2,2'-bipyridyl(Rudcbpy),bis-4,4'-(N-methylamide)-2,2'-bipyridyl(Rudamidebpy),bis-4,4'-(methyl)-2,2'-bipyr-idyl(RudMebPY), Ru(CO)(2)dcbpy(PPh3)(2)](2+)(Ru(2CO)dcbpy),and [Ru(H)(2)dcbpy(PPh3)(2)] (Ru(2H)dcbpy) have been studied by combined Density Functional/Time-Dependent Density Functional (DFT/TDDFT) techniques using different combinations of DFT exchange-correlation functionals and basis sets. PBE0/LANL2DZ provided more accurate geometries to describe S-0 whereas B3LYP/LANL2DZ predicted spectral energies that correlated better with the available experiment data. The Ru (II) complexes with different substituents emit photons ranging from 560 to 610 nm in the series RudMebpy, Rubpy, Rudamidebpy, Rudcbpy. The calculations predicted a maximum emission at about 540 nm for the complex constructed from two carbonyl pi-acceptors ligands trans to the dcbpy, while an emission in the far infrared region is calculated when two H sigma-donor ligands trans to the dcbpy. Our calculation results show correlations between HOMO-LUMO energy gap, Stokes shift, and T-1 distortion, which reflect the different effects of electron-withdrawing and donating groups. We proposed that these correlations can be used to predict the photophysical properties for new complexes. (C) 2019 Elsevier B.V. All rights reserved.
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