| 三个基于Cu2X2(X-=Cl-、Br-和I-)结构单元双核Cu(Ⅰ)配合物的合成、晶体结构、电子吸收和发射光谱 |
| Three Dinuclear Cu+ Complexes Based on Cu2X2 Core (X-=Cl-, Br- and I-): Syntheses, Crystal Structures, Absorption and Emission Spectra |
| 作者 | 单位 | E-mail | | 孙晓美 | State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing University of Technology, Nanjing 210009, China | | | 宁为华 | State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing University of Technology, Nanjing 210009, China | | | 刘建兰 | State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing University of Technology, Nanjing 210009, China | | | 刘少贤 | State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing University of Technology, Nanjing 210009, China | | | 郭平春 | State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing University of Technology, Nanjing 210009, China | | | 任小明 | State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing University of Technology, Nanjing 210009, China
State Key Laboratory & Coordination Chemistry Institute, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China | xmren@njut.edu.cn |
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| 摘要: 合成并表征了3个含Cu2X2结构单元的双核Cu(Ⅰ)配合物[Cu2(μ-X)2(deebq)2](其中deebq=2,2'-联喹啉-4,4'-二甲酸乙酯;X=Cl(1),Br(2)or I(3))。化合物1～3同构,其晶体属三斜晶系,空间群为Pl,具有相似的晶胞参数和晶体堆积结构。Cu2X2双核单元具有反演中心对称性,每个Cu+与deebq配体中2个N原子、2个μ2桥联的卤素X-阴离子配位,形成扭曲的四面体配位环境。通过deebq配体中苯环间π…π堆积,相邻双核分子形成超分子一维链,超分子链间存在弱范德瓦尔斯引力。在二氯甲烷溶液中,3个化合物都存在1个宽而不对称的电荷迁移吸收带(500～630nm区域),其强度和位置不受桥联X-配体影响。因此,电荷迁移带归属为由Cu+中心到deebq配体的电荷转移。在二氯甲烷溶液中,3个化合物发射强荧光,发射带中心波长位于400nm处,该发射带归属为deebq配体内的π-π*电子跃迁。在固体以及二氯甲烷溶液中,都没观察到从金属中心到配体的MLCT发射带。 |
| 关键词: 2,2'-联喹啉-4,4'-二甲酸乙酯 双核配合物 晶体结构 MLCT 吸收光谱 发射光谱 |
| 基金项目: 国家自然科学基金(No.21071080)和江苏省自然科学基金(No.BK2010551)资助项目 |
| Abstract: Three dinuclear Cu+ complexes [Cu2(μ-X)2(deebq)2] (where deebq=4,4'-diethylester-2,2'-biquinoline; X=Cl (1), Br (2) or I (3)), have been synthesized and characterized spectroscopically. The isostructural 1～3 crystallize in triclinic system with space group Pl, and show quite similar lattice parameters and packing structures. Two Cu+ ions in a dinuclear unit are related to each other via an inversion center; each Cu+ ion are coordinated by two Natoms form one deebq ligand and two X- anions, which act as a μ2-bridge mode to link two Cu+ ions, to form a distorted tetrahedral coordination geometry. The dinuclear units are aligned into a supramolecular chain via the intermolecular π…π interactions between the neighboring phenyl rings in deebq ligands, and the supramolecular chains are held together through weakly intermolecular van der Waals forces. Three complexes exhibit a broad and asymmetric absorption band in the 500～630 nm range in CH2Cl2, this band is almost independent on the bridged X- ligand and not observed in the absorption spectrum of deebq in CH2Cl2, thus, it is assigned to MLCTfrom Cu+ center to deebq ligand. Complexes 1～3 emitted intense fluorescence with the center around 400 nm, this emission band is attributed to the π-π* electronic transition of deebq ligand. No MLCTemission was observed in the CH2Cl2 solution and the solid state for three complexes. CCDC: 888543, 1; 888542, 2; 888541, 3. |
| Keywords: 4,4'-diethylester-2,2'-biquinoline dinuclear complex crystal structure MLCT absorption spectra emission spectra |
| 投稿时间：2013-03-31 修订日期：2013-05-07 |
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| 孙晓美,宁为华,刘建兰,刘少贤,郭平春,任小明.三个基于Cu2X2(X-=Cl-、Br-和I-)结构单元双核Cu(Ⅰ)配合物的合成、晶体结构、电子吸收和发射光谱[J].无机化学学报,2013,29(10):2176-2182. |
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