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(英文)

Synthesis and Characterization of Chiral 2,5-Bis(4,5-pinene-2-pyridyl) Pyrazine and Its Rhenium(Ⅰ) Complex

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）3CI（L）]- DMF were synthesized. X-ray crystallographic analysis show that L crystallizes in monoclinic P21 space group while [Re （CO）3C1 （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 （Cll）. Both ligand and [Re（CO）3CI（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.