Synthesis of novel pyridyl containing phospholanes and their polynuclear luminescent copper(i) complexes

• DOI: 10.1039/c5dt03346b
• Publication Date: 2015-11-16T16:01:18Z
• Authors: E. I. Musina; A. V. Shamsieva; I. D. Strelnik; T. P. Gerasimova; D. B. Krivolapov; I. E. Kolesnikov; E. V. Grachova; S. P. Tunik; C. Bannwarth; S. Grimme; S. A. Katsyuba; A. A. Karasik; O. G. Sinyashin
• Keywords: 01 natural sciences; 0104 chemical sciences

A novel type of cyclic P,N-ligands, pyridyl containing phospholanes, has been synthesized in a moderate yield by the reaction primary phosphines with 1,4-dichlorobutane superbasic medium. series homo tetranuclear octahedral Cu4I4L2, dinuclear tetrahedral Cu2I2L3, and "head-to-tail" Cu2I2L2 luminescent complexes these ligands were obtained. All compounds characterized using range spectroscopic computational techniques, case some Cu4I4L2 Cu2I2L3 complexes, single crystal X-ray diffraction. The structural diversity obtained was reflected their photophysical properties: phosphorescence spectra display emission broad spectral 471-615 nm. TD-DFT computations allow assignment band around 550 nm for 471 complex to vertical triplet-singlet transition from metal-to-ligand halide-to-ligand charge-transfer (3)(M + X)LCT excited state, whereas second at 600 assigned predominantly Cu4I4 cluster-centered ((3)CC) state.