Accesses to electronic structures and the excited states of blue luminescent copper(I) complexes containing N-heterocyclic carbene ligands: a DFT/TDDFT exploitation.

The ground electronic states and photophysical properties of three designed Cu(I) complexes [Cu(ImNHC)(POP)](+) (1), [Cu(methyl-ImNHC)(POP)](+) (2), and [Cu(BenzImNHC)(POP)](+) (3); where [ImNHC = 3-methyl-1-(pyridin-2-yl)-1H-imidazol-2-ylidene; methyl-ImNHC = 3-methyl-1-(pyridin-2-ylmethyl)-1H-imidazol-2-ylidene; BenzImNHC = 3-methyl-1-(pyridin-2-yl)-1H-benzimidazol-2-ylidene], have been investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The results reveal that the presence of the methylene spacer in the NHC ligands has a more direct effect on the distribution of frontier molecular orbitals while the elongation of π conjugation provided by the fused imidazole in the NHC ligands has a negligible effect. The UV-vis absorption spectra of all the complexes are well produced by TD-DFT calculations based on the charge transfer amount calculations and the corresponding band assignments are discussed. Importantly, the triplet energy calculations demonstrated that complex 2 would be a highly efficient blue emitter with the deep-blue of 440 nm.