Journal
DALTON TRANSACTIONS
Volume 45, Issue 5, Pages 2250-2260Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5dt03346b
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Funding
- St. Petersburg State University [12.50.24.2014]
- Russian Foundation for Basic Research [14-03-31302_mol_a]
- German Academic Exchange Service (DAAD) [91577762, 91589283]
- government of the Republic of Tatarstan Algarish
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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 ((CC)-C-3) excited state.
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