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• 166330-10-5 bis[2-(diphenylphosphino)phenyl] ether 
• 66-71-7 1,10-Phenanthroline 

Relevant academic research and scientific papers

Speeding-up Thermally Activated Delayed Fluorescence in Cu(I) Complexes Using Aminophosphine Ligands

Luminescent copper(I) complexes presenting thermally activated delayed fluorescence (TADF) have drawn attention as emitters for organic light emitting diodes (OLEDs). While the majority of ligands used have nitrogen as donor atoms, in this work, we report the synthesis and characterization of three copper(I) complexes with the diimine ligand 1,10-phenanthroline and aminophosphine-derived ligands containing the piperazine and N,N’-dimethylethylenediamine to evaluate their effect into the emission properties. The photophysical studies as a function of temperature suggested TADF and phosphorescence emission, supported by detailed density functional theory (DFT) calculations. The use of aminophosphine ligands enhance the TADF decay pathway in comparison with copper complex containing the usual POP ligand. These properties, combined with the appropriate HOMO-LUMO energy levels and thermal stability, make these compounds a promising alternative for application in OLEDs.

Reducing lifetime in Cu(i) complexes with thermally activated delayed fluorescence and phosphorescence promoted by chalcogenolate-diimine ligands

Luminescent copper(i) complexes have drawn attention due to their promising performance as alternative optoelectronic materials to the well-known heavy transition metal complexes. Herein, we report the synthesis of six luminescent Cu(i) complexes with phosphines and 1,10-phenanthroline-derived ligands with thiadiazole and selenodiazole groups in order to evaluate the effect of the heavy atom on their photophysical properties. Steady-state and time-resolved spectroscopy confirmed delayed fluorescence emission via a thermally activated delayed fluorescence mechanism in all cases. The experimental spectroscopic data were analyzed with detailed quantum-chemical calculations. Interestingly, these complexes did not show the expected heavy atom effect that enhances the spin-orbit coupling matrix elements, but nevertheless the addition of the heavier chalcogens contributed to reducing the photoluminescence lifetime to roughly 800 ns, which is the lowest reported so far for such TADF materials. This journal is

Heteroleptic Copper(I)-Based Complexes for Photocatalysis: Combinatorial Assembly, Discovery, and Optimization

A library of 50 copper-based complexes derived from bisphosphines and diamines was prepared and evaluated in three mechanistically distinct photocatalytic reactions. In all cases, a copper-based catalyst was identified to afford high yields, where new heteroleptic complexes derived from the bisphosphine BINAP displayed high efficiency across all reaction types. Importantly, the evaluation of the library of copper complexes revealed that even when photophysical data is available, it is not always possible to predict which catalyst structure will be efficient or inefficient in a given process, emphasizing the advantages for catalyst structures with high modularity and structural variability.

Geometric and electronic properties in a series of phosphorescent heteroleptic Cu(I) complexes: Crystallographic and computational studies

We have investigated the electronic and geometric structures in the lowest excited states of six phosphorescent heteroleptic [CuI(NN)(DPEphos)]+(DPEphos?=?bis[(2-diphenylphosphino)phenyl]ether) complexes with varying NN?=?diimine ligand structures using density functional theory. In comparison to the ground state, the results show a decrease of the dihedral angle between the N–Cu–N and P–Cu–P planes for these excited states with mixed ligand-to-ligand (DPEphos lone pair?→?π?(NN)) and metal-to-ligand charge transfer (dπ(Cu)?→?π?(NN)) character. Sterically less demanding ligands facilitate this process, which is accompanied by a geometric relaxation of the DPEphos ligand and contraction of the Cu–N bonds. The density functional for the excited state calculations has been selected based on ground state validation studies. We evaluated the ability of seven density functionals to reproduce the molecular ground state geometries and absorption spectra obtained by single-crystal X-ray diffraction and solution-phase UV–Vis absorption spectroscopy respectively. Standard methods (PBE and B3LYP), which do not account for dispersion, systematically overestimate internuclear distances. In contrast, approaches including dispersion (B97D3, PBE0-GD3, M06L, M06, ωB97XD) remove this systematic effect and give less expanded molecular structures. We found that only the hybrid functionals (B3LYP, PBE0-GD3, M06), incorporating a portion of exact exchange from Hartree–Fock theory, accurately predict the experimental absorption energies.

Heteroleptic copper(I) complexes prepared from phenanthroline and bis-phosphine ligands

Preparation of [Cu(NN)(PP)]+ derivatives has been systematically investigated starting from two libraries of phenanthroline (NN) derivatives and bis-phosphine (PP) ligands, namely, (A) 1,10-phenanthroline (phen), neocuproine (2,9-dimethyl-1,10-phenanthroline, dmp), bathophenanthroline (4,7-diphenyl-1,10-phenanthroline, Bphen), 2,9-diphenethyl-1,10-phenanthroline (dpep), and 2,9-diphenyl-1,10-phenanthroline (dpp); (B) bis(diphenylphosphino) methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3- bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), 1,1′-bis(diphenylphosphino)ferrocene (dppFc), and bis[(2- diphenylphosphino)phenyl] ether (POP). Whatever the bis-phosphine ligand, stable heteroleptic [Cu(NN)(PP)]+ complexes are obtained from the 2,9-unsubstituted-1,10-phenanthroline ligands (phen and Bphen). By contrast, heteroleptic complexes obtained from dmp and dpep are stable in the solid state, but a dynamic ligand exchange reaction is systematically observed in solution, and the homoleptic/heteroleptic ratio is highly dependent on the bis-phosphine ligand. Detailed analysis revealed that the dynamic equilibrium resulting from ligand exchange reactions is mainly influenced by the relative thermodynamic stability of the different possible complexes. Finally, in the case of dpp, only homoleptic complexes were obtained whatever the bis-phosphine ligand. Obviously, steric effects resulting from the presence of the bulky phenyl rings on the dpp ligand destabilize the heteroleptic [Cu(NN)(PP)]+ complexes. In addition to the remarkable thermodynamic stability of [Cu(dpp)2]BF4, this negative steric effect drives the dynamic complexation scenario toward almost exclusive formation of homoleptic [Cu(NN)2]+ and [Cu(PP)2]+ complexes. This work provides the definitive rationalization of the stability of [Cu(NN)(PP)]+ complexes, marking the way for future developments in this field.

Electrophosphorescent homo- and heteroleptic copper(I) complexes prepared from various bis-phosphine ligands

Homo- and heteroleptic copper(i) complexes obtained from various chelating bis-phosphine ligands and Cu(CH3CN)4BF4 have been used for the preparation of light emitting devices. The Royal Society of Chemistry.

Simple Cu(I) complexes with unprecedented excited-state lifetimes

This report describes new, readily accessible copper(I) complexes that can exhibit unusually long-lived, high quantum yield emissions in fluid solution. The complexes are of the form [Cu(NN)(POP)]+ where NN denotes 1,10-phenanthroline (phen), 2