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

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摘要 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)º, V = 8504.3(2) Å3, Z = 4, Mr = 1693.21, Dc = 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.

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	康丽菊
	陈进
	滕腾
	陈旭林
	余荣民
	卢灿忠

关键词 ： binuclear Cu(I) complex, crystal structure, emissive property, DFT calculation

Abstract：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)º, V = 8504.3(2) Å3, Z = 4, Mr = 1693.21, Dc = 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.

Key words： binuclear Cu(I) complex crystal structure emissive property DFT calculation

收稿日期: 2015-04-10 出版日期: 2015-11-11

基金资助:

This project was supported by the National Natural Science Foundation of China (51172232)

通讯作者: czlu@fjirsm.ac.cn E-mail: czlu@fjirsm.ac.cn

引用本文:

康丽菊;陈进;滕腾;陈旭林;余荣民;卢灿忠. Synthesis, Crystal Structure and Photoluminescence of a Cuprous Dimer with Tetrakis(pyrazol-i-yl)borate Linker[J]. 结构化学, 2015, 34(11): 1761-1767.
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. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2015, 34(11): 1761-1767.

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http://manu30.magtech.com.cn/jghx/CN/ 或 http://manu30.magtech.com.cn/jghx/CN/Y2015/V34/I11/1761

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