手性配体2,5-二(4,5-蒎烯-2-吡啶)吡嗪及其铼配合物的合成与表征

摘要

本文报道了手性配体2,5-二(4,5-蒎烯-2-吡啶)吡嗪(L)及其铼配合物[Re(CO)3Cl(L)]· DMF的合成与表征.X射线单晶衍射分析表明配体L晶体为单斜P21空间群,而配合物[Re(CO)3Cl(L)]· DMF晶体为正交P212121空间群.配合物[Re(CO)3Cl(L)]· DMF中铼原子与配体中的2个氮原子、3个羰基中的碳原子以及1个氯原子配位.CD谱和VCD谱测试表明,配体和配合物都表现出光学活性.受光激发时,配体和配合物分别在420和650 nm处发光.配体和配合物都具有二阶非线性光学性质,其二阶非线性光学效应分别为尿素的0.4和0.3倍.%The chiral ligand 2,5-bis(4,5-pinene-2-pyridyl) pyrazine (L) and its rhenium(Ⅰ) complex [Re(CO)3Cl(L)]·DMF were synthesized.X-ray crystallographic analysis show that L crystallizes in monoclinic P21 space group while [Re (CO)3Cl (L)]-DMF crystallizes in orthorhombic P212121 space group.The Re(Ⅰ)atom is six-coordinated by two nitrogen atoms (N1,N2) from the chiral ligand,three carbon atoms (C1,C2 and C3) from CO,and one chlorine atom (Cl1).Both ligand and [Re(CO)3Cl(L)]· DMF show optical activity as manifested by the CD and VCD spectra.Upon excitation,the ligand and Re(Ⅰ) complex emit at 420 and 650 nm,respectively.Both the ligand and Re(Ⅰ) complex show second-order non-linear optic (NLO) properties,and the second harmonic generation (SHG) responses are ～0.4 and ～0.3 times that of urea,respectively.CCDC:921976,complex; 921977,ligand.