Journal
INORGANIC CHEMISTRY
Volume 55, Issue 5, Pages 2157-2164Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.5b02546
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Funding
- National Natural Science Foundation of China [U1404209, 21372112, 21173113, 51373190]
- Natural Science Foundation of Henan Education Department, China [13A150804]
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Two luminescent cationic heteroleptic four-coordinate Cu-I complexes supported by N-heterocyclic carbene ligand and diphosphine ligand were successfully prepared and characterized. These complexes adopt typical distorted tetrahedral configuration and have high stability in solid state. Quantum chemical calculations show carbene units have contributions to both highest occupied molecular orbitals and lowest unoccupied molecular orbitals of these Cu-I-NHC complexes, the lowest-lying singlet and triplet excitations (S-0 -> S-1 and S-0 -> T-1) of [Cu(Pyim)(POP)(PF6) are dominated by metal-to-ligand charge transfer (MLCT) transition, while the S-0 -> S-1 and S-0 -> T-1 excitations of [Cu(Qbim)(POP)] (PF6) are mainly MLCT and ligand-centered transitions, respectively. These Cu-I-NHC complexes show efficient long-lifetime emissions (lambda(em) = 520 nm, tau = 79.8 mu s, Phi = 0.56 for [Cu(Pyim)(POP)](PF6), lambda(em) = 570 nm, tau = 31.97 mu s (78.99%) and 252.2 mu s (21.01%), Phi = 0.35 for [Cu(Qhim)(POP)](PF6)) in solid state at room temperature, which are confirmed as delayed fluorescence by investigating the emissions at 77 K.
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