Citation: KANG Li-Ju, CHEN Jin, TENG Teng, CHEN Xu-Lin, YU Rong-Min, LU Can-Zhong. Synthesis, Crystal Structure and Photoluminescence of a Cuprous Dimer with Tetrakis(pyrazol-i-yl)borate Linker[J]. Chinese Journal of Structural Chemistry, ;2015, 34(11): 1761-1767. doi: 10.14102/j.cnki.0254-5861.2011-0763 shu

Synthesis, Crystal Structure and Photoluminescence of a Cuprous Dimer with Tetrakis(pyrazol-i-yl)borate Linker

a.
a. Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 35002, China;
b.
b. Graduate University of Chinese Academy of Sciences, Beijing 100049, China;
c.
c. College of Life Science, University of Fujian Agriculture and Forestry, Fuzhou 350002, China

Received Date: 18 April 2015
Available Online: 19 May 2015
Fund Project: This project was supported by the National Natural Science Foundation of China (51172232) (51172232)

A cuprous dimer [Cu(POP)]₂(pz₄B)BF₄·(CH₃CN)₃ (1, POP=bis(2-(diphenylphos-phanyl)phenyl)ether, pz₄B^-=tetrakis(pyrazol-i-yl)borate anion) was synthesized from the reaction of Cu(CH₃CN)₄BF₄, POP and Kpz₄B in CH₃CN at room temperature. The compound was characterized by elemental analysis and X-ray single-Crystal structure analysis. It crystallizes in monoclinic, space group P2₁/c with a=12.3491(2), b=20.8845(3), c=33.0657(4) Å, β=94.251(1)°, V=8504.3(2) Å³, Z=4, M_r=1693.21, D_c=1.322 g/cm³, F(000)=3496, μ=1.843 mm^-1, GOOF=1.031, the final R=0.0442 and wR=0.1235 for 14397 observed reflections with I>2σ(I). 1 is an ionic compound. It is composed of a BF₄-anion and a {[Cu(POP)]₂(pz₄B)}⁺ cation. The cation contains two [Cu(POP)]⁺ cationic moieties and a pz₄B^- anionic linker. The Cu(I) ions show a distorted tetrahedral coordination geometry defined by two nitrogen atoms from a pz₄B^- bridging ligand and two phosphorous atoms from a POP terminal chelating ligand. The complex emits blue luminescence with the maximum peak at 457 nm with 3% quantum yield in solid state at room temperature. The Cu(I) centers are essentially electronically separated because both HOMO and LUMO contain very little contribution from the bridging ligand. The unexpected low emission is ascribed to the intramolecular interaction of the emissive centers.
- binuclear Cu(I) complex,
- crystal structure,
- emissive property,
- DFT calculation
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