三(苯并咪唑-2-亚甲基胺)锌配合物的晶体结构和量化计算

Crystal Structure and Quantum Chemistry Calculation of Zn(II) Complex with Tris(benzimidazol-2-ylmethyl)amine

以三(苯并咪唑-2-亚甲基胺)(NTB)为配体合成了ZnNTB·(NO3)2·DIPY·DMF(DIPY:4,4'-联吡啶)的单核锌配合物,用X-射线衍射法对其晶体结构进行了测定.晶体学参数:C37H36N12O7Zn,Mr=826.16,triclinic,a=0.9856(3)nm,b=1.2655(4)nm,c=1.5965(5)nm,α=81.714(5)o,β=76.601(5)o,γ=81.504(5)o,V=1.9032(10)nm3,Dc=1.442g/cm3,Z=2,F(000)=856,μ=0.712mm-1,空间群为P-1.采用经典的邻苯三酚自氧化法,对配合物进行了活性测试,其pI50值为4.21,说明该配合物具有拟SOD活性.利用G98量子化学程序包,在B3LYP/LanLDZ基组水平上对配合物C37H36N12O7Zn进行量子化学计算,对其分子轨道能量、电荷分布和前线轨道的贡献分析可知,所合成的配合物能与超氧阴离子自由基反应,与活性测试结果相符.

A new Zn(II) mononuclear complex with tris(benzimidazol2ylmethyl)amine (NTB) was synthesized with stoichiometry of ZnNTB·(NO3)2·DIPY·DMF (DIPY: 4,4'dipyridyl). The crystal structure was determined by using Xray diffraction method. The results showed that this complex belonged to the triclinic system, space group was P1 with a=0.985 6(3) nm, b=1.265 5(4) nm, c=1.596 5(5) nm, α=81.714(5)o,β=76.601(5)o,γ=81.504(5)o,V=1.903 2(10) nm3, Dc=1.442 g/cm3, Z=2, F(000)=856, μ= 0.712 mm-1. This complex had certain biological activity by means of classical pyrogallol autoxidation and its pI50 was 4.21. So it was called a model compound of superoxide dismutase (SOD). A quantum chemisry calculation using G98 with B3LYP/LanL2DZ basis sets was performed for the compound of C37H36N12O7Zn. The molecular orbital energies, atomic net charges, some frontiermolecular orbital components and population(%) were obtained. The results showed that the compound was able to inhibit superoxide radical and was consonant with the result of biological activity assay.