摘要:
在甲醇和二氯甲烷的混合溶剂中合成了2个新的铜(Ⅰ)配合物,[Cu(bdppmapy)(2,2'-bipy)]BF4(1)和[Cu(bdppmapy)(2,2'-bipy)]Ⅰ (2)(bdppmapy=N,N-二苯基膦甲基-2-氨基吡啶,2,2'-bipy=2,2'-联吡啶),通过X射线单晶衍射、元素分析、核磁共振氢谱、磷谱、荧光光谱和太赫兹时域光谱对2个配合物进行了分析和表征.1是由[Cu(CHaCN)4]BF4,bdppmapy和2,2'-bipy以1∶1∶1的比例混合得到的单核配合物.中心Cu(Ⅰ)离子通过与双膦配体(bdppmapy)以及含氮配体(2,2'-bipy)的螯合作用形成变形四面体结构.与1相似,2由CuI,bdppmapy和2,2'-bipy以1∶1∶1的比例混合得到.在配合物2的非对称单元中,bdppmapy和2,2'-bipy配体分别与中心铜(Ⅰ)离子螯合.荧光光谱表明所有的发射峰均源于金属-配体的荷移跃迁(MLCT).太赫兹时域光谱的应用也为配合物研究提供了有用的信息.%Two novel copper(Ⅰ) complexes [Cu(bdppmapy)(2,2'-bipy)]BF4 (1) and [Cu(bdppmapy)(2,2'-bipy)]Ⅰ (2) (2,2'-bipy=2,2'-bipyridine,bdppmapy=N,N-bis((diphenylphosphino)methyl)-2-pyridinamine) have been synthesized in mixed solvents of CH3OH and CH2C12 (1∶1,V/V) and characterized by single-crystal X-ray diffraction,elemental analysis,IR,1H NMR and 31P NMR spectroscopy,fluorescence spectra and THz time domain spectroscopy (THz-TDS).Complex 1,a mononuclear complex,was generated by the reaction of [Cu(CH3CN)4]BF4 and bdppmapy with 2,2'-bipy in 1∶1∶1 molar ratio.In complex 1,the central Cu(Ⅰ) forms a distorted tetrahedral geometry by coordinating with the diphosphine ligand (bdppmapy) and chelating N-donor ligand (2,2'-bipy).Like 1,2 was obtained by the reaction of CuI and bdppmapy with 2,2'-bipy in 1∶1∶1 molar ratio.In the asymmetric unit of 2,the bdppmapy and 2,2'-bipy ligands chelate central Cu(Ⅰ),respectively.The luminescent spectra show that the emission mechanism is metal-to-ligand charge transfer (MLCT).The application of terahertz time-domain spectroscopy also provides useful information for the research of complexes.CCDC:1874582,1;1874583,2.