CAJ | 학술논문

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1H NMR、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是中心对称的舣核Cu(Ⅰ)配合物,中心离子Cu(Ⅰ)采取扭曲四而体空间构型,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0.306 0 nm,大于两个铜原子的范德华半径之和,因此不存在Cu-Cu相瓦作用.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.
합성료일충신배체N,N-이[(이분기련)갑기]-2-필정알(L)급기쌍핵동(Ⅰ)배합물(CuBrL)2(1),채용1H NMR、흡수광보、질보화원소분석등방법대화합물진행표정,병통과X사선단정연사학정배합물1적정체결구.해정체결구속삼사정계,P-1공간점군.배합물1시중심대칭적의핵Cu(Ⅰ)배합물,중심리자Cu(Ⅰ)채취뉴곡사이체공간구형,분별여배체L적량개P원자화량개교련적Br원자배위;기중Cu-Cu거리위0.306 0 nm,대우량개동원자적범덕화반경지화,인차불존재Cu-Cu상와작용.밀도범함이론(DFT)계산표명1적HOMO전자밀도주요집중우동화서소원자,이LUMO전자밀도분포재배체(L)상.연구공작표명,배합물1적최저능급격발태통과금속도배체전하약천(MLCT)화서소도배체적전하약천(XLCT)량충궤제형성.
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).