溶剂分子调控基于多元醇胺协同二元线型羧酸构建MOFs的设计合成与吸附性能研究

Much attention has been paid to the synthesis of metal-organic frameworks (MOFs), not only because of their tremendous potential in structural design and truncation, but also because of the important applications such as catalysis, gas absorption and molecular recognition from their variable channels. It is well known that the construction of MOFs can often be modified by carefully selecting metal centres and elaborately designing suitable organic ligands as well as attaching the functional groups on their parents. However, the fact that solvent molecules can partake in the construction of MOFs has only received little attention. The aim of this project is to explore those MOFs involved in alcohol coordination and to achieve the solvent-dependent design and synthesis of MOFs under the synergistic use of polyalcohol amines and linear organic bicarboxylates. The effective incorporation of polyalcohol amines with linear organic bicarboxylates into secondary building units (SBUs) may give rise of the available coordination points which can make alcohol molecules accessible. We hope to synthesize novel MOFs materials with intrinsic structural evolution in a rational way from different alcoholthermal reactions. The difference in alcohol molecules results in different coordination ability for methanol, ethanol and propanol. The study on host-guest chemistry would define those resultant complexes with outstanding properties in selective adsorption as excellent candidates for sorbent materials.

金属有机骨架结构(Metal-Organic Frameworks: MOFs)配合物具有可设计和可裁剪性，通过定向修饰可以获得不同尺寸的孔道并赋予其催化、吸附和分子识别等方面的应用，因而引起人们极大的研究兴趣。过去人们研究主要集中在金属中心和配体的选择以及配体上官能团的修饰进行设计合成，很少注意到参与结构的溶剂分子。本申请旨在寻求醇溶剂分子参与配位的基于多元醇胺协同二元线型羧酸组装MOFs配合物的溶剂热可控合成及其吸附性能研究。充分利用多元醇胺协同羧酸构建的次级结构单元（Secondary Building Units, SBUs）具有可利用的金属配位点，从而为醇溶剂分子参与MOFs结构提供更多的机会。拟用简单变换醇溶剂分子导致其不同配位能力的方法，由甲醇到乙醇再到丙醇，设计控制合成具有新型内在结构演变的MOFs微孔材料，并通过主客体化学研究从中遴选出具有很好选择吸附性能的材料。

金属有机骨架结构(Metal-Organic Frameworks: MOFs)配合物具有可设计和可裁剪性，因其在催化、吸附和分子识别等方面的应用，引起人们极大的研究兴趣。本项目主要聚焦多元醇胺协同二元羧酸构建MOFs的可控合成与性能研究。重点从两个具体的影响因素阐述MOFs的可控合成及相关性能，即溶剂分子调控和氢键超分子自组装。在研究中，通过醇溶剂热的合成手段获得了一系列MOFs配合物，并利用x-ray射线衍射分析进行了单晶结构表征。研究表明这些化合物从双核到五核不等，甚至可扩展到一维无限核簇，空间上从零维到三维皆有，结构丰富多变。我们从上述的两个影响因素论证结构多变的规律，获得了比较满意的结论。同时，对部分化合物进行了理化表征，研究了相关的气体吸附性能、磁性行为以及荧光光谱，这些数据都对开发多功能配合物有较好的指导意义。相关结果部分已发表在一些国际晶体学专业杂志上。