Syntheses of Innovative Porous Metal Complexes and Their Functional Chemistry

在这个项目中，我们的目标是开发具有多孔配位聚合物(PCPS)特征的功能，如可设计的表面官能度、高规则性和骨架灵活性通过制备专用于乙炔氢原子的孔表面来实现高度可控的乙炔在微孔配位聚合物中的调节。乙炔的密度可以达到限值的200倍，而不会发生爆炸。利用同步辐射X射线衍射仪和第一性原理计算结果对吸附分子进行了直接观察，发现吸附在纳米孔中的双氢键载体对吸附的乙炔分子具有高度的稳定性。我们设计并合成了一种具有两种通道的双峰微孔双互穿PCP，分别对阴离子N(CN)2-和中性水分子具有两种通道。脱水骨架为较小的N_3-阴离子提供了游离态N(CN)_2-的特殊阴离子交换和选择性气体吸附的双重功能。N3-交换的骨架导致两个互穿骨架的相互位置错位，导致其中一个通道的有效孔径增加，吸附容量比合成的骨架更大。少量取代的乙炔在具有柱层结构的PCP的一维纳米通道中自发聚合。在该聚合体系中，只有带吸电子基团的单取代乙炔才能在通道中聚合。表明单体与骨架表面的羧酸部分之间的强氢键作用是引发聚合的关键因素。

In this project, we aim to develop functions with the characteristics of porous coordination polymers (PCPs)such as designable surface functionality, high regularity, and framework flexibility Highly controlled acetylene accommodation in a microporous coordination polymer has been accomplished by preparing a pore surface specific for acetylenic hydrogen atoms. The acetylene can be packed 200 times as densely as the limitation value without explosion. The adsorbed acetylene molecules are highly stabilized by the double hydrogen bonded supports in nanosized pores, which mere revealed by direct observation of the adsorbed molecules using the results of in-situ synchrotron XRD measurements and by first principles calculations.We have designed and synthesized a bimodal microporous twofold interpenetrating PCP with two types of channel for anionic N(CN)2- and neutral water molecules, respectively. The dehydrated framework provides a dual function of specific anion exchange of free N(CN)2- for the smaller N3- anions and selective gas sorption. The N3--exchanged framework leads to a dislocation of the mutual positions of the two interpenetrating frameworks, resulting in an increase in the effective pore size in one of the counterparts of the channels and a higher accommodation of adsorbate than in the as-synthesized framework.A few substituted acetylenes spontaneously polymerized in one-dimensional nanochannels of PCPs with pillared layer structure. In this polymerization system, only mono-substituted acetylenes with electron-withdrawing group could be polymerized in the channels. suggesting that strong hydrogen bonding interaction between the monomers and surface carboxylate moiety in the frameworks is a key factor to initiate the polymerization.