有机骨架带电的孔洞配位聚合物晶态材料的制备及性能研究

Porous coordination polymers are proving to be an exciting class of materials with potential applications in gas adsorption and ion exchange.In order to improve their performance,it is essencial to modify their surface functionalization of pores to strengthen the interactions between the pore surface and gas molecules or counter ions.Pyridinium ligands with charged organic skeleton is a class of excellent ligands, because they provide a means of strengthening the binding of gas molecules or counter ions through electrostatic forces. On the basis of our previous studies for the coordination polymers with semi-rigid bicarboxyl pyridinium ligands,we design three rigid bicarboxyl pyridinium ligands with different length and charge, which can further react with metal ions or metal clusters (referred to as secondary building units) with specific geometries to form porous coordination polymers. If the porous coordination polymers contain counter anions, we will investigate their ion exchange property, or we will explore their gas adsorption property. In addition, we will further research the influence of size of pores and quantity of charge on the gas adsorption and ion exchange, which will be helpful for their practical applications.

孔洞配位聚合物晶态材料具有气体吸附和离子交换两方面性能。为了提高这些性能，关键是要对孔洞表面进行功能化修饰，增强孔洞表面与吸附分子或离子间的作用力。吡啶盐配体有机骨架永久带电，可通过较强的静电作用力与气体分子或离子发生作用，是一类优秀的功能化配体。本项目在我们前期半刚性双羧基吡啶盐的研究基础上，拟使用三个不同长度和电荷的双羧基吡啶盐刚性配体与具有特定配位构型的金属中心或金属簇二级建造基元合成骨架结构稳定的孔洞配位聚合物。根据孔洞配位聚合物是否含有抗衡阴离子分别研究其气体吸附和离子交换性能，并根据实验结果详细探讨孔洞大小和骨架带电多少对气体吸附和离子交换性能的影响，为孔洞配位聚合物晶态材料的实际应用作出贡献。

有机骨架带电配位聚合物晶态材料的制备及性能研究是当前配位化学领域研究热点之一。带电桥联配体的存在赋予了该类材料永久存在的库仑极化力，使得它在吸附、离子交换及催化方面具有潜在的应用前景。本项目围绕着有机骨架带电这一核心问题，设计合成了3个带电桥联配体，并探讨了它们与金属盐反应合成带电配位聚合物晶态材料的合成条件。目前已成功制得14个结构新颖的此类配合物，并详细研究了它们的结构、热稳性、光学性质和催化性质。部分成果已经整理发表。