Triply Linked Corrole Dimers

The oxidation of 10–10′ singly linked corrole dimers with DDQ at low concentration in CHCl₃ afforded meso–meso, β–β, β–β triply linked 2H‐corrole dimers (with two inner NH groups in each corrole unit), which exhibited characteristic ¹H NMR and absorption spectra attributable to their nonaromatic electronic networks. These 2H‐corrole dimers were reduced with NaBH₄ to aromatic 3H‐corrole dimers, which were unstable and easily oxidized back to the 2H‐corrole dimers upon exposure to air. Bis(zinc(II)) complexes of the 2H‐corrole dimers were synthesized and characterized as rare examples of nonaromatic zinc(II) corrole complexes.     

溶剂对镓Corrole光谱性质的影响

合成了一系列周边取代的Corrole(1, 2, 3, 4)及其镓配合物1-Ga(Py)、2-Ga(Py)、3-Ga(Py)、4-Ga(Py),通过核磁共振氢谱(¹H NMR), 紫外-可见光谱, 电喷雾离子质谱(ESI-MS)的方法对其进行了表征. 研究了不同溶剂对这一系列自由Corrole 及镓Corrole 的紫外-可见(UV-Vis)吸收光谱, 稳态荧光和时间分辨荧光光谱, 将获得的荧光衰减动力学曲线采用单指数拟合并进行解卷积处理获得荧光的寿命值. 非（弱)极性溶剂对镓Corrole 紫外光谱的影响服从Bayliss 方程, 且镓Corrole 非辐射能量损失hc(ν¹_A-ν_F)与F(n)呈线性相关.     

The Corrole Radical

The reaction of 5,10,15‐trimesitylcorrole (H₃cor) with tungsten hexachloride and tungsten hexacarbonyl resulted in the unexpected formation of the 3,17‐dichloro‐5,10,15‐trimesitylcorrole radical (H₂cor*) as an air‐stable product. X‐ray crystallography proved the planarization of the corrole radical structure, which was rationalized by the reduced steric hindrance of two versus three hydrogen atoms inside the N₄ cavity. Although the aromaticity was lost, no specific changes in C? C or C? N bond distances could be observed. The regioselectivity of the two‐fold chlorination is the result of the nucleophilic attack of chloride ions to an oxidized corrole macrocycle, and is supported by DFT results. The corrole radical acts as a dianionic ligand and allows the insertion of the divalent zinc(II) cation, which usually does not form neutral corrole complexes.     

Corrole锰-氧配合物的稳定性研究

对5,10,15-三(五氟苯基)-Corrole(tpfc)Mn(V)≡O配合物的稳定性进行了研究. 以二氯甲烷溶剂为参考,乙醇、正辛醇、乙醚、四氢呋喃、二甲基亚砜、甲苯能加速(tpfc)MnV≡O的衰减,而N’N二甲基甲酰胺、水、乙酸乙酯、丙酮能减缓(tpfc)MnV≡O的衰减. (tpfc)MnV≡O与盐酸、醋酸反应生成(tpfc)MnIV-Cl、(tpfc)MnIV-O2CCH3. (tpfc)MnIII能与咪唑、四甲基咪唑、吡啶形成1:1的配合物,轴向配位常数按Imidazole >4-Methylimidazole >Py顺次减弱,在这些轴向配体存在时,(tpfc)MnV≡O的稳定性显著降低. 轴向配体与(tpfc)MnIII的结合导致其MnIII/MnIV半波电位降低. XPS实验结果显示(tpfc)MnIII与轴向配体结合后,其中心金属锰的结合能Mn2p3/2减少,减少程度与轴向配体的给电子能力有关.     

三苯基Corrole及其铜配合物的π-π堆积效应研究

Aggregation behavior of 5,10,15-tris(pentafluorophenyl)corrole (F₁₅TPC), 5,10,15,20-tetra(pentafluoroph-enyl)porphyrin (F₂₀TPP), and their copper complexes in DCM solution were investigated by using UV-Vis spectro-scopic method. F₂₀TPP and F₂₀TPPCu exhibited strong π-π stacking interactions in DCM, and the intermolecular dimerization constants turned out to be 1.82 × 10³ and 17.2 × 10³ L·mol^-1 respectively. However, extinction coefficients of F15TPC and F15TPCCu at soret band remained unchanged with increasing in their concentrations from 1.0 to 40.0 μmol·L^-1, indicating they remained monomeric in DCM solution. Based on DFT calculation and the π-π stacking geometries observed in crystal structures of metal octaethylcorrole complexes, destroy of π-π interactions in F₁₅TPC and F₁₅TPCCu may be understood by the electrostatic potential surfaces (EPS) features of the molecules and steric repulsions caused by the introducing of three phenyl at the meso- positions of corrole macrocycle.     

咔咯钴(Ⅲ)配合物与DNA的相互作用及抗肿瘤活性

合成了10-(4-羟基苯基)-5,15-二(五氟苯基)咔咯钴(Ⅲ)配合物(1-Co)和10-(4-吩噻嗪苯基)-5,15-二(五氟苯基)咔咯钴(Ⅲ)配合物(2-Co),并采用核磁共振波谱、质谱和紫外-可见光谱等对其结构进行了表征,利用紫外光谱、荧光光谱、圆二色谱、黏度测试和琼脂糖凝胶电泳等技术研究了配合物1-Co和2-Co与小牛胸腺DNA(ct-DNA)之间的相互作用.结果表明,配合物1-Co和2-Co与DNA之间的作用模式为外部结合,且在光照下均能引发DNA断裂.细胞毒性实验结果表明,配合物1-Co和2-Co具有很低的暗细胞毒性,但在光照条件下均能有效抑制H460,He La,A549等肿瘤细胞株增殖,表明配合物1-Co和2-Co在光动力治疗中具有潜在的应用价值.细胞核染色和线粒体膜电位检测结果表明,在光照条件下配合物2-Co可能是通过氧化损伤线粒体的途径抑制肿瘤细胞增殖.     

Corrole光敏剂在光动力治疗中的重原子效应

最近, 我们合成了一系列Corrole衍生物, 经过鼻咽癌(Nasopharyngeal carcinoma,NPC) 细胞的体外PDT试验后, 筛选出了一个具有优良PDT活性的Corrole光敏剂. 本文报道该类Corrole光敏剂在PDT中的重原子效应.