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（pcp）特征的功能，如可设计的表面功能，高规则性和框架灵活性，通过制备乙炔氢原子专用的孔表面，在微孔配位聚合物中实现了高度控制的乙炔容纳。乙炔的填充密度可达到限定值的200倍而不发生爆炸。利用原位同步加速器x射线衍射（XRD）测量结果和第一性原理计算对吸附的分子进行了直接观察，结果表明，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双峰微孔双互穿PCP，它具有两种通道，分别为阴离子N(CN)2-和中性水分子。脱水骨架具有自由N(CN)2-的特定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相互位置的错位，导致其中一个通道对应的有效孔径增加，并且比合成的骨架具有更高的吸附质容纳能力。一些取代乙炔在具有柱状层结构的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可以在通道中聚合。表明单体与骨架中表面羧酸基之间的强氢键相互作用是引发聚合反应的关键因素。

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.