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Structural, spectroscopic and DFT theoretical studies of phosphorescent CuIP 2 S‐containing cuprous complexes
Author(s) -
Liang Yu,
Wang Jian-Teng,
Song Li,
Dai Ding-Qiu,
Wang You-Yu,
Chai Wen-Xiang
Publication year - 2021
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s2053229621005696
Subject(s) - phosphorescence , ligand (biochemistry) , crystallography , chemistry , excited state , luminescence , thiourea , copper , molecule , iodide , photoluminescence , density functional theory , inorganic chemistry , materials science , computational chemistry , fluorescence , atomic physics , organic chemistry , biochemistry , physics , receptor , optoelectronics , quantum mechanics
Luminescent cuprous complexes are important coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The structures of two CuIP 2 S‐type cuprous complexes, namely, iodido(thiourea‐κ S )bis(triphenylphosphane‐κ P )copper(I), [CuI(CH 4 N 2 S)(C 18 H 15 P) 2 ] or [CuI(TU)(TPP) 2 ] ( I ), and (2,3‐dihydrobenzimidazole‐2‐thione‐κ S )iodidobis(triphenylphosphane‐κ P )copper(I), [CuI(C 7 H 6 N 2 S)(C 18 H 15 P) 2 ] or [CuI(DHBIT)(TPP) 2 ] ( II ), are described. In these two structures, the complex molecules of both are constructed by one copper(I) centre, one iodide ion, two TPP ligands and one thione ligand (TU for I and DHBIT for II ). The copper(I) centres of I and II are both located in a distorted CuIP 2 S tetrahedron and are coordinated by two P atoms from two TPP ligands, one S atom from the thione ligand and the I atom. The UV–Vis absorption and photoluminescence properties of these CuIP 2 S‐type cuprous complexes have been studied using crystalline powder samples. Detailed time‐dependent density functional theory (TD‐DFT) calculations and wavefunction analysis reveal that the pale‐blue–green phosphorescence emission should originate from intra‐ligand (TPP for I and DHBIT for II ) charge transfer, with a small component of the metal‐to‐ligand charge transfer 3 (IL+ML)CT excited state.