Synthesis and luminescence properties of the four-coordinate N-heterocyclic carbene (NHC) copper(I) complexes with different bisphosphine ligands
Journal of Molecular Structure, ISSN: 0022-2860, Vol: 1285, Page: 135504
2023
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Article Description
Here, we report a series of the four-coordinate N-heterocyclic carbene (NHC) copper(I) complexes having the same bidenate NHC ligand and different bisphosphine (P^P) ligands, [Cu(CNbenPy-benzIm)(Naphphos)]PF 6 ( P1 ), [Cu(CNbenPy-benzIm)(cyc-xantphos)]PF 6 ( P2 ), and [Cu(CNbenPy-benzIm)(xantphos)]PF 6 ( P3 ), (CNbenPy-benzIm = 3-(3-cyanobenzyl)-1-(5-phenylpyridin-2-yl)-1 H -imidazolylidene; BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene; cyc-xantphos = (9,9-dimethyl-9 H -xanthene-4,5-diyl)bis(dicyclohexylphosphine), xantphos = 9,9-dimethyl-9 H -xanthene-4,5-diyl)bis(diphenylphosphine)). P1 exhibits the metal-to-ligand charge transfer (MLCT) absorption band at 366 nm with high molar extinction coefficient of 2.44 × 10 4 M −1 cm −1, while P2 and P3 show a blue-shift of the MLCT absorption band at 336–341 nm with the molar extinction coefficients of 0.82–1.16 × 10 4 M −1 cm −1, which are just a little lower than that of P1. The emission wavelengths of all NHC-Cu(I) complexes can be fine-tuned to cover the spectral range of 525–555 nm with the phosphorescent origin in PMMA films. P1 has the lowest photoluminescence efficiency of 5.50% with the red-shifted emission wavelength at 555 nm and the emission lifetime of 237 μs, whereas P3 show the highest photoluminescence efficiency of 39.5% with the blue-shifted emission wavelength at 525 nm and the emission lifetime of 64.4 μs. The differences for photophysical properties of NHC-Cu(I) complexes were rationalized using density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations.
Bibliographic Details
http://www.sciencedirect.com/science/article/pii/S0022286023006014; http://dx.doi.org/10.1016/j.molstruc.2023.135504; http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=85151677305&origin=inward; https://linkinghub.elsevier.com/retrieve/pii/S0022286023006014; https://dx.doi.org/10.1016/j.molstruc.2023.135504
Elsevier BV
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