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Article Dans Une Revue Comptes Rendus. Chimie Année : 2012

Structures and spectral properties of heteroleptic copper (I) complexes: A theoretical study based on density functional theory

Résumé

The structures and electronic absorption spectra of newly synthesized heteroleptic copper (I) complexes [CuL1L2](+) (L-1 = phen-imidazole and/or L-2 = dipyrido[3,2-a:2',3'-c] phenazine derivatives) are analyzed under the light of density functional theory (DFT) and time-dependent DFT (TD-DFT). The ground states geometries, characterized by pi-stacking interactions, have been optimized using PBE-D functional taking into account dispersion correction. The UV-visible theoretical absorption spectra have been calculated using B3LYP functional in vacuum and taking into account solvent corrections by means of the polarized continuum model (PCM). Whereas the PBE-D functional is well adapted to the determination of the structures, it does underestimate drastically the transition energies. The spectra are characterized by high density of states, mainly metal-to-ligand-charge-transfer (MLCT) and intra-ligand (IL), between 600 nm and 250 nm. Most of the complexes show an intense band in the near-UV energy domain (similar to 320 nm) corresponding to an IL transition. The lowest part of the absorption spectra, starting at 600 nm, corresponds to MLCT transitions leading to a shoulder observed experimentally between 400 and 500 nm. The upper part of the spectra, beyond 300 nm, puts in evidence strong mixing between ligand-to-ligand-charge-transfer (LLCT), IL and MLCT states. (C) 2011 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

Domaines

Chimie

Dates et versions

hal-02142703 , version 1 (28-05-2019)

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Citer

Megumi Kayanuma, Narayan Bera, Martina Sandroni, Yann Pellegrin, Errol Blart, et al.. Structures and spectral properties of heteroleptic copper (I) complexes: A theoretical study based on density functional theory. Comptes Rendus. Chimie, 2012, 15 (2-3, SI), pp.255-266. ⟨10.1016/j.crci.2011.10.010⟩. ⟨hal-02142703⟩
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