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N,N-二[(二苯基膦)甲基]-2-吡啶胺溴化铜(Ⅰ)配合物的合成和光谱
引用本文:迟绍明,张俊峰,卞兆勇,傅文甫.N,N-二[(二苯基膦)甲基]-2-吡啶胺溴化铜(Ⅰ)配合物的合成和光谱[J].光谱学与光谱分析,2010,30(5).
作者姓名:迟绍明  张俊峰  卞兆勇  傅文甫
作者单位:1. 中国科学院理化技术研究所,北京,100190;中国科学院研究生院,北京,100049;云南师范大学化学化工学院,云南,昆明,650092
2. 云南师范大学化学化工学院,云南,昆明,650092
3. 中国科学院理化技术研究所,北京,100190
摘    要:合成了一种新配体N,N-二(二苯基膦)甲基]-2-吡啶胺(L)及其双核铜(Ⅰ)配合物(CuBrL)2(1),采用1HNMR、吸收光谱、质谱和元素分析等方法对化合物进行表征,并通过X射线单晶衍射确定配合物1的晶体结构。该晶体结构属三斜晶系,P-1空间点群。配合物1是中心对称的双核Cu(Ⅰ)配合物,中心离子Cu(Ⅰ)采取扭曲四面体空间构型,分别与配体L的两个P原子和两个桥联的Br原子配位;其中Cu-Cu距离为0.3060nm,大于两个铜原子的范德华半径之和,因此不存在Cu-Cu相互作用。密度泛函理论(DFT)计算表明1的HOMO电子密度主要集中于铜和卤素原子,而LUMO电子密度分布在配体(L)上。研究工作表明,配合物1的最低能级激发态通过金属到配体电荷跃迁(MLCT)和卤素到配体的电荷跃迁(XLCT)两种机制形成。

关 键 词:铜(Ⅰ)  双核配合物  光谱  吡啶胺  密度泛函理论  Copper(Ⅰ)

Synthesis and Spectra of Copper(Ⅰ) Bromide Complex with N,N-Bis[(Diphenylphosphino) Methyl]-2-Pyridinylamine
CHI Shao-ming,ZHANG Jun-feng,BIAN ghao-yong,FU Wen-fu.Synthesis and Spectra of Copper(Ⅰ) Bromide Complex with N,N-Bis[(Diphenylphosphino) Methyl]-2-Pyridinylamine[J].Spectroscopy and Spectral Analysis,2010,30(5).
Authors:CHI Shao-ming  ZHANG Jun-feng  BIAN ghao-yong  FU Wen-fu
Abstract:A new ligand N,N-bis(diphenylphosphino)methyl]-2-pyridinylamine (L) and its luminescent dinuclear copper(Ⅰ)complex CuBrL]2 (1) were synthesized and characterized by mass spectrometry,elemental analysis,NMR and electronic spectroscopies.The structure of complex 1 was determined by X-ray crystal analysis to be a dinuclear complex with a pseudo-tetrahedral geometry.The complex 1 crystallizes in a triclinic space group P-1 and has two copper(Ⅰ) centers bridged by two halogen ligands to form the dinuclear structure with a four-membered Cu2 Br2 ring.The Cu-Cu distance in complex 1 is 0.306 0 nm which is longer than a sum of Van der Waals radius of two copper(Ⅰ) atoms.Therefore there is no substantial interaction between the two copper(Ⅰ) centers in complex 1.DFT calculations indicate that the electron density of HOMO is distributed mainly over the copper,bromine and phosphorus atoms,while that of LUMO is localized on the ligand.Our work shows that there are two mechanisms to form the the lowest excited state of complex 1,i.e.the metal-to-ligand charge transfer (MLCT) and halogen-toligand charge transfer (XLCT).
Keywords:Dinuclear complexes  Spectroscopy  Aminopyridine  DFT
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