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Preparation of Microporous Molecular Crystals Having Hydrogen-Bonded Networks and Their Application to Functional Organic Materials

氢键网络微孔分子晶体的制备及其在功能有机材料中的应用

基本信息

批准号：
06403022
负责人：
AOYAMA Yasuhiro
金额：
$ 18.88万
依托单位：
KYUSHU UNIVERSITY (1995-1996)Nagaoka University of Technology (1994)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1996
项目状态：
已结题

项目摘要

An anthracene bisresorcinol derivative 1 has been shown to form molecular sheets composed of hydrogen-bonded polyresorcinol chains together with large cavities roofed and floored by the anthracene rings. The cavities selectively incorporate a variety of guest molecules.(1) Diels-Alder Reaction As Catalyzed by Microporous Crystal 1As confirmed before, crystal 1 incorporates two molecules of ethyl acetate and benzene in each cavity. When the guest molecules are changed respectively into acrolein (dienophile) and 1.3-cyclohexadiene, a facile and catalytic Diels-Alder reaction takes place in a highly stereoselective (endo-selective) manner, where the roles of 1 as a microporous catalyst are (a) to assemble two reactants in the cavity, (2) to activate the dienophile via acid-catalysis through host-guest hydrogen-bonding, (3) to exert steric constraint in a 3D cavity, and (4) to exchange reactants and products in the cavity.(2) Functional Self-Assembly of 1D ChainsAnthracene monoresorcinol compound 2 forms similar but 1D hydrogen-bonded network. The chains are held together via intercalation of the orthogonal anthracene substituents ; in the cavities are included guest molecules in a 1 : 1 host-guest stoichiometry. The cavities are much less thick as compared with those in the 2D network of host 1 and show a novel thickness selectivity in the guest-binding, where a remarkable preference for linear alkyl groups to brached ones is observed. Closely packed anthracene-guest alternate columns can be constructed in this way.

蒽双间苯二酚衍生物1已显示形成由氢键键合的聚间苯二酚链连同由蒽环覆盖和包围的大空腔组成的分子片。空腔选择性地结合各种客体分子。(1)微孔晶体1催化的狄尔斯-阿尔德反应如前所述，晶体1在每个空腔中掺入两个乙酸乙酯和苯分子。当客体分子分别转化为丙烯醛（亲二烯体）和1，3-环己二烯的一个简单和催化的Diels-Alder反应在高度立体选择性的（内选择性）方式，其中1作为微孔催化剂的作用是（a）在空腔中组装两种反应物，（2）通过主客体氢键通过酸催化活化亲二烯体，（3）在3D空腔中施加空间约束，以及（4）在空腔中交换反应物和产物。(2)一维链的功能性自组装蒽单间苯二酚化合物2形成类似的一维氢键网络。链通过正交蒽取代基的插入保持在一起;在空腔中以1：1的主客体化学计量包括客体分子。的空腔是少得多的厚度相比，在2D网络的主机1，并显示出一种新的厚度选择性的客人绑定，其中观察到一个显着的偏好为线性烷基支链的。用这种方法可以构建紧密填充的蒽-客体交替柱。