Unusual fluorescence behaviour of a heteroleptic Cu(i) complex featuring strong electron donating groups on a diimine ligand
Date
Authors
SANHUEZA FRIGOLETT, JUAN MANUEL
Santander-Nelli, Mireya
Sanhueza, Luís Manuel
Navas, Daniel
Rossin, Elena
Natali, Mirco
Dreyse, Paulina A.
Santander-Nelli, Mireya
Sanhueza, Luís Manuel
Navas, Daniel
Rossin, Elena
Natali, Mirco
Dreyse, Paulina A.
Authors
Date
Datos de publicación:
10.1039/d1nj04811b
Keywords
Niobium - Phenanthroline - Charge Transfer - Copper Compounds - Fluorescence - Ligands - Luminescent Devices - Cu Complexes - Diimine Ligand - Diimines - Diphosphine Ligand - Diphosphines - Electron-donating Group - Fluorescence Behaviors - Heteroleptic - Phenyl Ethers - Synthesised - Excited States - Bathocuproine - Bis Diimine Copper Complex - Bis[2 (diphenylphosphino)phenyl]ether - Copper Complex - Diimine Diphosphine Copper Complex - Ligand - Niobium - Phenanthroline - Unclassified Drug - Acceleration - Article - Calculation - Comparative Study - Controlled Study - Electrochemical Analysis - Electron - Fluorescence - Geometry - Luminescence - Photochemistry - Physical Activity - Quantum Chemistry - Quantum Yield - Structure Analysis - Synthesis
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Abstract
A novel diimine ligand (N^Nb) and the corresponding heteroleptic diimine-diphosphine Cu(i) complex (Cu-N^Nb) have been synthesized and their structural properties characterized. The N^Nb ligand is [2,9-bis-[4-(dimethylamino)phenyl]ethenyl]-4,7-diphenyl-1,10-phenanthroline, which has a bulky structure designed to retain the tetrahedral geometry of the corresponding Cu(i) complex in the excited state in order to avoid potential quenching by flattening distortion. The corresponding Cu(i) complex comprises the mentioned diimine ligand and bis-[2-(diphenylphosphino)-phenyl]ether (POP) as the diphosphine ligand. The electrochemical and photophysical properties, suitably complemented by theoretical calculations, have been studied and compared to those of a reported heteroleptic Cu(i) complex including POP and bathocuproine as the diphosphine and diimine ligands, respectively. According to both experimental and computational data, the new complex Cu-N^Nb is characterized by an unexpected luminescence behaviour that markedly differs from those typically encountered in heteroleptic diimine-diphosphine Cu(i) complexes and stems from the direct, spin-allowed radiative decay (fluorescence) of an intraligand charge transfer excited state on the bulky diimine ligand. The emission quantum yield is also surprisingly high (35%), possibly inspiring potential and alternative applications of this novel complex in luminescent devices or imaging. This journal is © 2023 Elsevier B.V., All rights reserved.
Description
Keywords
Niobium , Phenanthroline , Charge Transfer , Copper Compounds , Fluorescence , Ligands , Luminescent Devices , Cu Complexes , Diimine Ligand , Diimines , Diphosphine Ligand , Diphosphines , Electron-donating Group , Fluorescence Behaviors , Heteroleptic , Phenyl Ethers , Synthesised , Excited States , Bathocuproine , Bis Diimine Copper Complex , Bis[2 (diphenylphosphino)phenyl]ether , Copper Complex , Diimine Diphosphine Copper Complex , Ligand , Niobium , Phenanthroline , Unclassified Drug , Acceleration , Article , Calculation , Comparative Study , Controlled Study , Electrochemical Analysis , Electron , Fluorescence , Geometry , Luminescence , Photochemistry , Physical Activity , Quantum Chemistry , Quantum Yield , Structure Analysis , Synthesis
Citation
10.1039/d1nj04811b