396723-75-4

Upstream product

• 484-11-7 2.9-dimethyl-1,10-phenanthroline 
• 166330-10-5 bis[2-(diphenylphosphino)phenyl] ether 

Downstream Products

• 1251536-84-1 [Cu(bis[2-(diphenylphosphino)phenyl]ether)(2,9-dimethyl-1,10-phenanthroline)](tetrakis(bis-3,5-trifluoromethylphenyl)borate) 

Relevant academic research and scientific papers

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.

Wide-Bite-Angle Diphosphine Ligands in Thermally Activated Delayed Fluorescent Copper(I) Complexes: Impact on the Performance of Electroluminescence Applications

We report a series of seven cationic heteroleptic copper(I) complexes of the form [Cu(P^P)(dmphen)]BF4, where dmphen is 2,9-dimethyl-1,10-phenanthroline and P^P is a diphosphine chelate, in which the effect of the bite angle of the diphosphine ligand on the photophysical properties of the complexes was studied. Several of the complexes exhibit moderately high photoluminescence quantum yields in the solid state, with φPL of up to 35%, and in solution, with φPL of up to 98%. We were able to correlate the powder photoluminescence quantum yields with the % Vbur of the P^P ligand. The most emissive complexes were used to fabricate both organic light-emitting diodes and light-emitting electrochemical cells (LECs), both of which showed moderate performance. Compared to the benchmark copper(I)-based LECs, [Cu(dnbp)(DPEPhos)]+ (maximum external quantum efficiency, EQEmax = 16%), complex 3 (EQEmax = 1.85%) showed a much longer device lifetime (t1/2 = 1.25 h and >16.5 h for [Cu(dnbp)(DPEPhos)]+ and complex 3, respectively). The electrochemiluminescence (ECL) properties of several complexes were also studied, which, to the best of our knowledge, constitutes the first ECL study for heteroleptic copper(I) complexes. Notably, complexes exhibiting more reversible electrochemistry were associated with higher annihilation ECL as well as better performance in a LEC.

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.

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.

Oxygen gas sensing by luminescence quenching in crystals of Cu(xantphos)(phen)+ complexes

We have shown that crystals of the highly emissive copper(I) compounds [Cu(POP)(dmp)]tfpb, [Cu(xantphos)(dmp)]tfpb, [Cu(xantphos)(dipp)]tfpb, and [Cu(xantphos)(dipp)]pftpb, (where POP = bis[2-(diphenylphosphino)phenyl]ether; xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; dmp = 2,9-dimethyl-1,10-phenanthroline; dipp = 2,9-diisopropyl-1,10-phenanthroline (dipp); tfpb- = tetrakis(bis-3,5-trifluoromethylphenylborate); and pftpb = tetrakis(pentfluorophenyl)borate) are oxygen gas sensors. The sensing ability correlates with the amount of void space calculated from the crystal structures. The compounds exhibit linear Stern-Volmer plots with reproducible KSV constants from sample to sample; these results reinforce the observations that the sensing materials are crystalline and the sensing sites are homogeneous within the crystals. The long lifetime (～30 μs), high emission quantum yield (β = 0.66), appreciable KSV value (5.65), and very rapid response time (51 ms for the 95% return constant) for [Cu(xantphos)(dmp)]tfpb are significantly better than those for the [Cu(NN) 2]tfpb complexes studied previously and compare favorably with [Ru(4,7-Me2phen)3](tfpb)2, (KSV = 4.76; 4,7-Me2phen = 4,7-dimethyl-1,10- phenanthroline). The replacement of precious metals (like Ru or Pt) with copper may be technologically significant and the new compounds can be synthesized in one or two steps from commercially available starting materials. The strictly linear Stern-Volmer behavior observed for these systems and the absence of a polymer matrix that might cause variability in sensor to sensor sensitivity may allow a simple single-reference point calibration procedure, an important consideration for an inexpensive onetime limited use sensor that could be mass produced.