A new application of terahertz time-domain absorption spectra in luminescent complexes: characterization of the C-Hπ...

Six Cu(i) complexes, [Cu(2,3-f)(bdppmapy)]BF4 (1), [Cu(2,3-f)(bdppmapy)]ClO4 (2), [Cu(2,3-f)(bdppmapy)]CF3SO3 (3), [Cu(imidazo[4,5-f])(bdppmapy)]BF4 (4), [Cu(imidazo[4,5-f])(bdppmapy)]ClO4 (5), and [Cu(imidazo[4,5-f])(bdppmapy)]CF3SO3·MeOH (6·MeOH) (bdppmapy = N,N-bis[(diphenylphosphino)methyl]-2-pyridinamine, 2,3-f = pyrazine[2,3-f][1,10]-phenanthroline, and imidazo[4,5-f] = 1H-imidazo[4,5-f][1,10]-phenanthroline), have been synthesized to explore the effects of counteranions on their crystal structures, photophysical properties, and terahertz (THz) spectra. Time-dependent density functional theory (TD-DFT) shows that the luminescence performance of these complexes is attributed to the metal-to-ligand charge transfer (MLCT) in combination with ligand-to-ligand charge transfer (LLCT). In complexes 1-3, the characteristic peak at 1.4 THz is mainly related to the C-Hπ interaction formed by the H atom on the 4#/5# position of 2,3-f and the benzene ring from the bdppmapy on the adjacent asymmetric unit. The common C-Hπ interaction enhances the rigidity of the structure and has non-negligible influence on the photoluminescence quantum yields (PLQYs): the stronger the C-Hπ interaction is, the higher the quantum yield (QY) is. In complexes 4-6, similar absorption peaks (1.10-1.30 THz) are mainly related to the C-Hπ interactions, and strong absorption peaks (1.50-1.90 THz) are affected by the typical hydrogen bonds N-HF/O and O-HO. These results show that some weak interactions can be characterized by THz time-domain spectroscopy (THz-TDS). So, the THz spectroscopy method would make it possible to tune some of the weak interactions in complex structures to regulate the luminescence of materials.