熊先炼,赵彦超,杨豹,黄廷洪.化学通报,2018,81(7):598-603. |
含π…π作用的双核Cu(I)配合物的合成、结构、理论计算与发光性质(英文) |
Synthesis, structure, theoretical studies and luminescent properties of a dinuclear copper complex withSπ-πSinteraction |
投稿时间:2018-01-01 修订日期:2018-03-15 |
DOI: |
中文关键词: 铜(I)配合物,晶体结构,π…π,DFT,发光性能 |
英文关键词:Copper(I) complex crystal structure π…π DFT luminescent properties |
基金项目:大学生创新创业训练计划项目(No.cx2016038), 四川理工学院人才引进项目(No. 2017RCL21),四川省教育厅重点项目(No. 18ZA0338),广西北部湾海洋灾害研究重点实验室培育基地(钦州学院)开放课题(No. 2017KF04),材料腐蚀与防护四川省重点实验室开放基金项目(No. 2015CL03) 资助 |
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中文摘要: |
合成了铜(I)配合物 [Cu2(bpe)(2,2’-bipyridine)2(PCHO)2] (BF4)2 (1),并利用X-射线单晶衍射仪测定了化合物的结构。晶体结构研究表明:配合物1 中存在2个独立配位中心,每个Cu+离子中心以N3P模式进行配位,形成扭曲四面体构型;π…π相互作用导致一维和二维π堆积结构的形成。DOS和 PDOS研究显示:配合物的HOMO轨道主要与中心Cu+离子、2-二苯基膦苯甲醛 和 2,2’-联吡啶有关;LUMO轨道主要与1,2-二(4-吡啶基)乙烯有关。DFT计算显示能带宽度为1.64 eV。此外,配合物1 在365 nm有紫外吸收峰,归属为dπ–π*吸收;在508 nm有荧光发射峰,归属为MLCT跃迁。 |
英文摘要: |
A copper(I) complex, [Cu2(bpe)(2,2’-bipyridine)2(PCHO)2] (BF4)2 (1) (PCHO = o-(diphenylphos phino)benzaldehyde), have been synthesized and characterized by X-ray crystal structure analysis.. The structural analysis shows that the complex consists of two crystallographically independent Cu(I) center, and the Cu+ cation is four coordinate N3P, forming a distorted-tetrahedral geometry, and π…π interactions result in the construction of 1D π-chain and 2D π-stacking network. DOS and PDOS studies indicate that the HOMOs are mainly dominated by the copper d-orbital with admixed PCHO and 2,2’-bipyridine ligand character, while the LUMOs predominantly consist of the π-electron system of bpe. DFT calculation shows the energy gap is 1.64 eV. The UV–Vis spectrum shows that a broad peak at 365 nm is attributed to dπ–π* absorption. Moreover, the copper (I) complex exhibits weak photoluminescence in acetonitrile solution (508 nm), which is on the order expected for a MLCT transition. CCDC: 1412208, 1 |
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