Issue 5, 2016

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

Abstract

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

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

Supplementary files

Article information

Article type
Paper
Submitted
28 août 2015
Accepted
16 nov. 2015
First published
16 nov. 2015

Dalton Trans., 2016,45, 2250-2260

Author version available

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

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 and O. G. Sinyashin, Dalton Trans., 2016, 45, 2250 DOI: 10.1039/C5DT03346B

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