Analysis of vibrational spectra (FT-IR and VCD) and nonlinear optical properties of [Ru(L)3]2+ complexes

Density functional theory calculations were performed on [Ru(L) 3 ] 2+ (L = 1,10-phenanthroline, 2,2′-bipyridine, 2,2′-bipyrimidine, 2,2′-bipyrazine) complexes by employing B3PW91 functional and LAN2DZ basis set to predict their spectra and nonlinear optical response. The geometrical and coordinatio...

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Bibliographic Details
Published in:Journal of coordination chemistry 2014-10, Vol.67 (20), p.3288-3310
Main Authors: Islam, Nasarul, Pandith, Altaf Hussain
Format: Article
Language:English
Subjects:
Coordination energy
Density function theory
Enantiomers
Hyperpolarizability
Ruthenium
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Summary:Density functional theory calculations were performed on [Ru(L) 3 ] 2+ (L = 1,10-phenanthroline, 2,2′-bipyridine, 2,2′-bipyrimidine, 2,2′-bipyrazine) complexes by employing B3PW91 functional and LAN2DZ basis set to predict their spectra and nonlinear optical response. The geometrical and coordination energy studies explained that the stability of [Ru(L) 3 ] 2+ metal complexes depends on the extent of interaction of the dπ orbitals of Ru 2+ with the π* ligand orbitals, which is maximum for 1,10-phenanthroline. The two enantiomers of the [Ru(L) 3 ] 2+ show IR absorption peaks in the region of 1100-1800 cm −1 , and a slight shift occurs to lower frequency by solvent. The vibrational circular dichroism peaks of [Ru(phen) 3 ] 2+ had major contribution from out-of-phase stretching of 1,10-phenanthroline rings and a minor contribution from H-C=C-H wagging and C=C stretching of rings. Maximum hyperpolarizability was observed for [Ru(phen) 3 ] 2+ due to stronger anharmonicity in the π-electron system. Among the [Ru(L) 3 ] 2+ (L = bpy, bpm, and bpz) complexes, [Ru(bpm) 3 ] 2+ shows enhanced hyperpolarizability due to increase in the dipole along the X-direction. In derivative Ru 2+ complexes, we found that hyperpolarizability depends on electron-donating capability of the substituent. As per FMOs study, the HOMO is predominantly metal fragment based, the LUMO is primarily ligand based, and the larger value of hyperpolarizability corresponds to the lower E LUMO -E HOMO gap, reflecting that nonlinear optical response is a consequence of additive dipolar responses of charge transfer and hyperpolarizability.
ISSN:0095-8972
1029-0389
DOI:10.1080/00958972.2014.961921