2015): Copper(I)-1,1,1-tris(diphenylphosphinomethyl)ethane complexes with different coordination modes tuned by auxiliary ligands and their spectroscopic properties, Journal of Coordination Chemistry, Three mono-, bi-and tetranuclear copper(I) complexes, [Cu(phen)(triphos-O)]BF 4 (1) (phen = 1,10-phenanthroline, triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane), [Cu 2 (bipy)(triphos) 2 ](BF 4 ) 2 (2) (bipy = 4,4′-bipyridine), and [Cu 4 (MeOC^N^N) 4 (triphos) 2 (bipy)](BF 4 ) 4 (3) (MeOC^N^N = 6-(4-methoxyphenyl)-2,2′-bipyridine), have been synthesized and characterized by NMR spectroscopy, electrospray ionization, and matrix-assisted laser desorption ionization time-of-flight mass spectrometries, elemental analysis, and X-ray crystal analysis. The crystal structure investigation revealed the copper ions of the complexes have pseudo-tetrahedral coordination geometry. The electronic absorption spectra of 1, 2, and 3 contain low-energy bands at 350-500 and 400-650 nm, which are assigned to d(Cu) → π*(phen or bipy) and a mixture of d(Cu) → π*(MeOC^N^N) and d(Cu) → π* (bipy) transitions, respectively. Complex 2 displays a strong, long-lived solid-state emission with a maximum at 555 nm and lifetime of 13.6 μs at room temperature. Photoinduced electron-transfer properties of 2 and 3 involving nanosecond time-resolved absorption spectroscopy and electron spin resonance techniques were studied.

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A novel triply bridged dinuclear four-coordinate Copper(I) Complex with sterically bulky bis(dicyclohexylphosphino)methane ligand * E-mail: wf_fu@yahoo.com.cn Abstract: A novel triply bridged dinuclear copper(I) complex: Cu 2 (µ-paa)(µ-dcpm) 2 (BF 4 ) 2 ·2CH 2 Cl 2 [ paa = pyridine-2-carbaldehyde azine (C 12 H 10 N 4 ) and dcpm = bis(dicyclohexylphosphino)methane(C 25 H 46 P 2 ) ] has been synthesized and structurally characterized. Crystallographic studies of the complex showed that two copper(I) ions were bridged by one paa ligand and two dcpm ligands. The paa ligand adopted the Z configuration at the partially double N-N bond and the two copper ions have distorted tetrahedral coordination geometry.Because of the steric effect of dcpm, the pyridine rings of the paa ligand are obviously not on the same plane (the dihedral angle is 43.61 0 ). The interaction between neighboring ligands results in a N-N bond length (1.374(7) Å) contraction. The UV-vis spectra of the complex exhibited intense high-energy absorptions at λ max < 340 nm and broad visible bands in a range of 380-550 nm, ascribed to intraligand (IL π-π*) transitions and metal-to-ligand charge-transfer (MLCT) transitions, respectively. Interestingly, the absorbtion peaks varied regularly with the solvent polarity. Although the complex has a rigid structure with the copper ions held firmly by triply bridged ligands, the emission and excitation spectra revealed that the complex exhibits weak fluorescence. Warsaw and Springer-Verlag Berlin Heidelberg. © Versita

The title polymeric copper(I) complex, {[Cu2(4,4′‐azpy)(μ‐paa)(C18H15P)2](BF4)2}∞, [4,4′‐azpy = di‐4‐pyridyl­diazene (C10H8N4) and paa = pyridine‐2‐carb­aldehyde azine (C12H10N4)] has been prepared and the crystal structure determined. The copper(I) centres adopt a distorted tetrahedral coordination geometry and are linked through binucleating azpy and paa ligands.