Theoretical Studies on [Ru(bpy)₂(NN)]²⁺ [NN = Hydrazone and Azine]: Ground‐ and Excited‐State Geometries, Electronic Structures, Absorptions, and Phosphorescence Mechanisms

Abstract

Keywords: Ruthenium / Electronic structure / Spectroscopic properties / Density functional calculationsThe ground-and excited-state geometries, electronic structures, absorptions, and emissions of two ruthenium(II) complexes Ru(bpy) 2 (N ∧ N) [bpy = 2,2Ј-bipyridine, N ∧ N = hydrazone (1) and azine (2)] were investigated theoretically. Their ground and the excited state geometries were fully optimized at the B3LYP/MP2/LANL2DZ and UB3LYP/UMP2/LANL2DZ levels, respectively, and the calculated geometries are consistent with the X-ray results. At the TD-DFT level with the PCM model, the absorptions and phosphorescence properties of 1 and 2 were calculated on the basis of the optimized ground-and excited-state geometries, respectively. The calculated lowest-lying absorptions of 1 (512 nm) and 2 (598 nm) are attributed to a {[d

On the viability of cyclometalated Ru(ii) complexes as dyes in DSSC regulated by COOH group, a DFT study

“…[22][23][24] The calculations were carried out at B3LYP/LanL2DZ level of theory, 25,26 which is backed by previous investigations that the calculation at this level of theory can provide the converged geometrical parameters for numerous transition metal complexes. [27][28][29][30][31][32] From TD-DFT calculation, two quantities which are related to the UV-Vis spectra were obtained: the energy of the vertical electronic excitations (E n-m ) and the corresponding oscillator strength (f). On the basis of E n-m and f, the absorption spectra were afterwards simulated by using Gaussian functions, to have a intuitive comparison with the experimental data.…”

Design and theoretical study of phenothiazine-based low bandgap dye derivatives as sensitizers in molecular photovoltaics

“…Density functional theory (DFT) methods are a reliable tool to design and study new materials commonly used in DSSCs before synthesis. This allows systematic chemical modifications of the dye structure (Baryshnikov et al 2013;Minaev et al 2011;Liu et al 2008). Here, we designed and studied theoretically sixteen phenothiazine based dyes of PTZ 0 − 15 (Fig.…”