具有π共轭骨架的Salen-卟啉型同、异双核配合物的合成及谱学性质

设计合成了两类具有π共轭骨架的Salen-卟啉型配体及金属配合物. 以Salen-卟啉半体及相应的醛为原料, 运用金属模板法合成了单核镍和双核镍Salen-卟啉型金属配合物. 在单核镍的基础上可得到异双核镍、锌Salen-卟啉型金属配合物. 通过核磁共振氢谱(¹H NMR)、紫外-可见(UV-Vis)光谱、傅里叶变换红外(FTIR)光谱、电喷雾质谱(ESI-MS)和荧光光谱等多种谱学手段对其结构进行了表征. 研究表明, 单核镍及异双核镍、锌配合物中, 镍离子落入Salen 部分的配位空腔, 而锌离子则是与卟啉部分形成锌卟啉大环结构。由于卟啉环流效应及分子π共轭结构的影响, 导致配体上的氢原子的化学位移向高场或低场移动. 当金属离子与配体配位之后,卟啉部分的紫外-可见光谱的Soret带和Q带均发生显著变化, 而荧光则出现猝灭现象.

Synthesis and Spectral Properties of Salen-Porphyrin Type Homo- and Hetero-Binuclear Complexes with π-Conjugate Configuration

Two new types of Salen-porphyrin ligand and metal complexes with π-conjugate configurations were synthesized. The mono- and bi-nuclear nickel Salen-porphyrin complexes were synthesized from half Salen-porphyrin ligands and the corresponding aldehyde by metal templating. Based on the mononuclear nickel Salen-porphyrin complexes, the heterobinuclear nickel, zinc Salen-porphyrin complexes were synthesized. All the compounds were characterized by proton nuclear magnetic resonance (¹H NMR), ultraviolet-visible (UV-Vis) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, electron spray ionization mass spectrometry (ESI-MS), and fluorescence spectroscopy. These results indicate that the nickel ion is located in the cavity of the Salen part, while the zinc ion is located in the center of the porphyrin part of the mononuclear nickel and heterobinuclear nickel-zinc Salen-porphyrin complexes. The circumfluent effect of the porphyrin and the π-conjugate configuration resulted in the chemical shifts of the hydrogen atoms moving to a higher or lower field. The positions of the Soret and Q bands in the UV-Vis spectrum of the porphyrin change after the metal ion coordinated. Furthermore, the fluorescence quenched due to the metal ion.