Dependence between luminescence properties of Cu(i) complexes and electronic/structural parameters derived from steric effects
Date
Authors
SANHUEZA FRIGOLETT, JUAN MANUEL
Santander-Nelli, Mireya
Cortés-Arriagada, Diego
Sanhueza, Luís Manuel
Dreyse, Paulina A.
Santander-Nelli, Mireya
Cortés-Arriagada, Diego
Sanhueza, Luís Manuel
Dreyse, Paulina A.
Authors
Date
Datos de publicación:
10.1039/d2nj00407k
Keywords
Copper Compounds - Ligands - Luminescence - Bulky Substituents - Cu Complexes - Heteroleptic - Luminescence Properties - N Ligands - N-ligands - Non-radiative - Phenyl Ethers - Steric Effect - Structural Parameter - Density Functional Theory - Alkene - Copper Complex - Diamine - Ligand - Phenyl Group - Article - Calculation - Chemical Structure - Comparative Study - Conformational Transition - Decomposition - Density Functional Theory - Geometry - Hydrogenation - Luminescence - Optics - Photoluminescence - Polymerization - Quantum Yield
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Abstract
A series of heteroleptic Cu(i) complexes of type [Cu(N^N)(POP)]+, with POP: bis-[2-(diphenylphosphino)-phenyl]ether and different phenanthroline-based N^N ligands were investigated using density functional theory (DFT) and time-dependent DFT (TD-DFT). The complexes comprise N^N ligands with different bulky substituents at the 2,9 positions, and the addition of phenyl substituents at the 4,7 positions is also investigated. Furthermore, in the complex with the bulkier N^N ligand, the effect of unsaturated hydrocarbon chains added and the presence of dimethylamine electron donor groups were analyzed. The composition/energies of the frontier orbitals and the emission energies were determined for all complexes. Besides, we evaluated the steric effects induced by different N^N ligands in electronic (Pauli repulsion energy) and structural (root-mean-square deviation) terms to determine their influence on the photoluminescence efficiency comparing the properties of the proposed Cu(i) complexes with four reported complexes. The analyzed data allow us to find simple relationships to predict the radiative (k<inf>r</inf>) and non-radiative (k<inf>nr</inf>) constants based on the steric effects that each complex undergoes according to the type of N^N ligand used, obtaining the best balance (higher k<inf>r</inf> and lower k<inf>nr</inf>) in complexes with bulkier substituents. Therefore, these complexes could be proposed as suitable luminescent materials for optical applications. © 2023 Elsevier B.V., All rights reserved.
Description
Keywords
Copper Compounds , Ligands , Luminescence , Bulky Substituents , Cu Complexes , Heteroleptic , Luminescence Properties , N Ligands , N-ligands , Non-radiative , Phenyl Ethers , Steric Effect , Structural Parameter , Density Functional Theory , Alkene , Copper Complex , Diamine , Ligand , Phenyl Group , Article , Calculation , Chemical Structure , Comparative Study , Conformational Transition , Decomposition , Density Functional Theory , Geometry , Hydrogenation , Luminescence , Optics , Photoluminescence , Polymerization , Quantum Yield
Citation
10.1039/d2nj00407k