一种有机酰腙类配体及其金属凝胶的结构及性能

设计合成了一种带有长链烷基和配位基团的新型有机配体2-吡啶甲醛-4'-十二烷氧基苯甲酰腙(简称L),并采用核磁(1H-NMR)、红外(FTIR)、电喷雾质谱(ESI-MS)和元素分析确认其结构.在乙醇和水的混合溶剂中,配体L可使溶剂凝胶化,并可与多种金属离子(Co(Ⅱ),Ni(Ⅱ),Zn(Ⅱ)和Cu(Ⅱ)作用,形成金属凝胶.采用扫描电镜分析表明,L自身形成的凝胶及金属凝胶的微观形貌均为相互搭接的纤维状结构.采用紫外光谱分析表明在乙醇溶液中L分子形成了聚集体.采用平板流变仪分析表明引入金属离子可提高凝胶的强度.进一步合成了L与Cu(Ⅱ)的配合物,通过对比配合物与金属凝胶的红外光谱和紫外光谱,证明金属凝胶中配体L与金属离子间形成了配位作用.

STRUCTURE AND PROPERTIES OF AN ORGANIC ACYLHYDRAZONE LIGAND AND ITS METALLOGELS

A novel organic ligand 2-pyridylaldehyde-4′-dodecyloxybenzoyl hydrazone(L) with a long alkyl chain and a coordination group was designed and synthesized.The molecular structure of L was confirmed by 1H nuclear magnetic resonance(1H-NMR) spectrum,Fourier-transform infrared(FTIR) spectrum,electrospray ionization-mass(ESI-MS) spectrum and elemental analysis(EA).L itself could gel the mixture of ethanol and water at suitable weight ratios to form white gels(defined as L gel) by mixing method.L could also gel the ethanol and water mixture with a series of metal ions,including Co(Ⅱ),Ni(Ⅱ),Zn(Ⅱ) and Cu(Ⅱ) to form metallogels.The SEM observation revealed that networks of fibers were formed in both the L gel and the Cu(Ⅱ) based metallogels.As indicated by the ultraviolet(UV) absorption spectra,the drastic decrease in the extinction coefficient at λmax as the concentration of L confirmed the formation of aggregates of L molecules in ethanol.The rheological properties of the gel samples were tested by plate rheometer.The metallogels displayed improved strength and gel stability compared to L gel at the same gel concentration.Furthermore,the coordination complex of L and Cu(Ⅱ) at molar ratio of 2∶1 was synthesized and confirmed by ESI-MS.According to the FTIR spectra and UV absorption spectra of the coordination complex and the CuAc2 based metallogel,the coordination between L and metal ions was found to exist in the metallogel.