title: 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 ((3)CC) excited state.
authors.affiliation: A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre of the Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, Russia. elli@iopc.ru.
authors.forename: E I
authors.initials: EI
authors.lastname: Musina
authors.forename: A V
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authors.lastname: Shamsieva
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authors.lastname: Strelnik
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authors.initials: TP
authors.lastname: Gerasimova
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authors.lastname: Kolesnikov
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authors.initials: EV
authors.lastname: Grachova
authors.forename: S P
authors.initials: SP
authors.lastname: Tunik
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authors.lastname: Grimme
authors.forename: S A
authors.initials: SA
authors.lastname: Katsyuba
authors.forename: A A
authors.initials: AA
authors.lastname: Karasik
authors.forename: O G
authors.initials: OG
authors.lastname: Sinyashin