Syntheses of Innovative Porous Metal Complexes and Their Functional Chemistry

在这个项目中，我们的目标是开发功能与多孔配位聚合物（PCPs）的特点，如可设计的表面功能，高度的规则性，和框架的灵活性。高度控制的乙炔在微孔配位聚合物的住宿已经完成了通过制备一个特定的孔表面的乙炔氢原子。乙炔可按极限值200倍的密度装填而不爆炸。通过同步辐射XRD原位测量和第一性原理计算，直接观察吸附分子，发现吸附的乙炔分子被纳米孔中的双氢键支撑物高度稳定.我们设计并合成了一种双峰微孔双层互穿PCP，它具有两种阴离子N（CN）2-和中性水分子通道.脱水的框架提供了一个双重功能的特定的阴离子交换游离N（CN）2-为较小的N3-阴离子和选择性气体吸附。N3-交换骨架导致两个互穿骨架的相互位置发生错位，导致其中一个通道对应物的有效孔径增大，对吸附质的容纳能力增强;少量取代乙炔在具有柱撑层结构的PCP一维纳米通道中自发聚合.在该聚合体系中，只有带有吸电子基团的单取代乙炔才能在孔道中聚合。这表明单体与骨架中表面羧酸基团之间的强氢键相互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.