摘要
合成了N,N′-亚水杨基喹哪啶酰肼(sqnhz)及其锰配合物[Mn(sqnhz)2]sqnhz(C51H39Cl2MnN9O6,Mr=999 75).X射线衍射实验结果表明:标题配合物晶体属于三斜晶系,空间群为P1;晶体学参数:a=0.7723(1)nm,b=1.1537(3)nm,c=1.3549(2)nm,α=74 387(8)°,β=83 342(6)°,γ=80 967(9)°,V=1 1448(4)nm3,Z=1,Dc=1 450mg/m3,F(000)=515,μ(Mo-Kα)=0.468mm-1,R=0 0606,Rw=0 1152.在配合物[Mn(sqnhz)2]中,锰(Ⅱ)原子具有扭曲的八面体配位构型,晶体通过分子间氢键作用形成一维无限链状结构.红外光谱表明,配体在形成配合物后,ν(CO)和ν(CN)红移.电子光谱表明存在π-π 和d-π 的跃迁,荧光光谱表明,配合物金属对配体n-π 激发引起的荧光发射峰有较大的影响,配合物对于λ=0.106nm激光倍频系数I2ω/I2ω(KDP)为0 94.
The title complex[Mn(sqnhz)_2]sqnhz(C_(51)H_(39)Cl_2MnN_9O_6,M_r=999.75),where sqnhz is N,N′-salicylidenequinaldoylhydrazide,has been synthesized.The complex belongs to monoclinic system,space group P1 with a=0.772 3(1)nm,b=1.153 7(3)nm,c=(1.354 9)(2)nm,α=74.387(8)°,β=83.342(6)°,γ=80.967(9)°,V=1.144 8(4)nm^3,(Z=1),D_c=1 450 mg/m^3,F(000)=515,μ(M_(o)-K_α)=0.468 mm^(-1),R=0.060 6,R_w=(0.115 2) for 2 198[I≥2σ(I)] observed reflections,GOF=0.960,(Δ/σ)_(mean,max)=0.002,(0.009),(Δρ)_(max,min)=276,-248 e nm^(-3).In the complex,the Manganese reveals a distorde octahedral coordination geometry and there is an one-dimensional chain structure through the intermolecular hydroges bonds,ν(CO)and ν(CN)are shifted to lower frequencies in IR spectra π-π~ charge transitions and d-π~ chargetransitions are observed in their electronic spectra.The emission lines(λ=310 nm)are shifted in fluorescence spectra.The second harmonic generation I_(2ω) of the complex is 0.94 time as that of KDP.
出处
《分子科学学报》
CAS
CSCD
2004年第3期47-55,共9页
Journal of Molecular Science
基金
福建省自然科学基金资助项目(E0210026)
福建省发展计划委员会项目([2002]161)
