Functional Chemistry of Guest-responsive Nano Space Created by Coordination Polymers

坚固的配位聚合物框架的出现表明固体配位化合物在多孔材料和膨胀材料导向的配位化学中占有重要地位。然而，这类化合物被认为是静态材料。如果我们利用配位聚合物的优势，我们可以提供具有柔性框架的动态材料，这就是所谓的第三代化合物。在本文中，我们重点关注与这种框架相关的柱状层基序，它不仅可以通过修改柱状模块创建通道大小和形状，还可以创建化学功能。在本文中，我们成功地设计并实现了一种新型柱状层状配位聚合物。1)采用柱状层框架合理合成所得化合物。利用该框架，我们成功地与1,2-二吡啶基糖苷（dpyg）建立了一个氢键通道，其相互作用仅用于具有氢键能力的更多的来宾。这种类型的框架是非常罕见的，具有双刃轴形基序的二维框架的配位聚合物也已由硫氰酸钴与N-（3-吡啶）异烟酰胺（3-pia）或N-（3-吡啶基）烟酰胺（3-pna）反应合成。通过在结构中动态切换酰胺基团，发现了伴随客体分子的晶体到晶体转变。2)该新型网络在客体蒸汽/还原气氛下表现出晶体到晶体的转变。3)最有趣的是“发现水或甲醇蒸气的滞回吸附特性”。骨架从载宿主到被吸附的转化是由与客体的氢键相互作用驱动的，这表明骨架对特定客体分子有反应，并将其微腔改变为适合客体分子形状和/或亲和力的微腔。这种独特的性质为材料定向配位化学开辟了一个新的维度。少

The advent of robust coordination polymer frameworks demonstrated that solid coordination compounds were acquiring an important position in porous materials and expanding materials-directed coordination chemistry.However, this sort of compounds are considered to be static materials.If we take advantages of coordination polymers, we could provide dynamic materials with flexible frameworks, which are so-called 3rd generation compound. In this manuscript we focus on a pillared-layer motif relevant for this sort of frameworks, which create not only a channel size and shape but also a chemical functionality simply by modifying the pillar module.In this manuscript, we succeeded in designing and realizing a new pillared-layer type coordination polymer.1) The obtained compound is rationally synthesized by using a pillared layer framework. By taking advantages of the framework, we succeeded in creating a hydrogen bonding channel with 1,2-dipyridylglycoI (dpyg), whose interaction is used only fo … More r guests having hydrogen bonding capability.This type of framework is very fewCoordination polymers with two-dimensional frameworks with a double-edged axe-shaped motif have also been synthesized from reactions of cobalt(II) thiocyanate with N-(3-pyridy) isonicotinamide (3-pia) or N-(3-pyridyl)nicotinamide (3-pna). Crystal-to-crystal transformation accompanying inclusion of guest molecules by dynamically switching amide groups in the structure has been found.2) This novel network exhibits a crystal to crystal transformation under guest vapor/reduced atmosphere.3) What is most interesting is "finding of hysteretic sorption properties" for water or methanol vapor. The framework conversion from the apohost to adsorbed one is driven by hydrogen bonding interaction with the guests, indicating that the framework responds to a specific guest molecule and changes its microcavities into those well-suited for the shape and/or affinity of the guest molecule. This unique properties opened up a new dimension to materials-directed coordination chemistry. Less