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Theoretical study of geometric, optical, nonlinear optical, UV–Vis spectra and phosphorescence properties of iridium(III) complexes based on 5-nitro-2-(2′,4′-difluorophenyl)pyridyl

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Abstract

In this work, we studied the structural, optical, nonlinear optical properties , absorption spectra and phosphorescence properties of four cyclometalated heteroleptic iridium complexes [Ir(dFNppy)2(PPh3)L] with dFNppy = 5-nitro-2-(2′,4′-difluorophenylpyridyl, PPh3 = triphenylphosphine, L = Cl− (1), NCS− (2), NCO− (3) and N3− (4) using DFT and TD-DFT methods. The electronic and geometrical structures of the S0 and T1 have been studied and compared. Experimental absorption bands were assigned on the basis of natural transition orbitales, and a good agreement with experience has been obtained. Phosphorescence wavelengths of the four complexes were calculated with vertical and adiabatic methods. Further, linear optical properties (mean polarizability \(\left\langle \alpha \right\rangle\), anisotropy polarizability \(\left| \alpha \right|\)), the static first hyperpolarizabilities electric-field-induced second harmonic generation \(\beta_{//} \left( { - 2\omega ;\omega ,\omega } \right)\) and the hyper-Rayleigh scattering (HRS) first hyperpolarizability \(\beta_{\text{HRS}} \left( { - 2\omega ;\omega ,\omega } \right)\)), and the depolarization ratio DR of these complexes are calculated by DFT with PBE0 functional in order to understand nonlinear optical properties. Higher polarizability \((\alpha )\) and first hyperpolarizabilities \((\beta )\) of these complexes are obtained. It is also observed an inverse correlation between the predicted β value and the HOMO–LUMO energy difference (Δε).

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  1. Laboratoire d’études physico-chimiques, University of Saida - Dr Moulay Tahar, Sidon, Algeria

    Mohamed Boukabene

  2. Department of Chemistry, University of Saida - Dr Moulay Tahar, Sidon, Algeria

    Houari Brahim, Djebar Hadji & Abdelkrim Guendouzi

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Boukabene, M., Brahim, H., Hadji, D. et al. Theoretical study of geometric, optical, nonlinear optical, UV–Vis spectra and phosphorescence properties of iridium(III) complexes based on 5-nitro-2-(2′,4′-difluorophenyl)pyridyl. Theor Chem Acc 139, 47 (2020). https://doi.org/10.1007/s00214-020-2560-9

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