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.

已经显示出蒽双甲硅醇衍生物1形成由氢键键合的多拉索尔链组成的分子片，以及大型的腔室，由炭疽环地板地板。腔选择性地结合了各种宾客分子。（1）由微孔晶体1A催化的Diels-Alder反应在每个腔中都掺入了两个分子乙酸乙酸乙酯和苯。当客人分子分别被更改为丙烯醛（二磷）和1.3环己二烯时，一种便捷的和催化性的Diels-alder反应发生在高度立体选择性（内部选择性）的方式中，其中1个作为1作为微量催化剂的角色（通过2）在cavity中的驱动器（2）dien dien（2）dien dien（2），以2）（2）激活（2），即2）激进（2），即2）（2）dien dien dien dien dien dien dien dien dien dien dien dien dien dien dien（2）氢键，（3）在3D腔中施加空间约束，（4）在空腔中交换反应物和产物。（2）1D链氨基链氨甲氨基酚单诺尔醇化合物的功能自组装相似，但1D氢键键合。链条通过正交蒽取代基的插入在一起。在1：1的宿主 - 宿主化学计量学中，腔中包括宾客分子。与宿主1的2D网络中的腔相比，腔体的厚度要小得多，并且在宾客结合中显示出新颖的厚度选择性，在这里，观察到线性烷基而不是撑压烷基的偏好。可以以这种方式构建紧密包装的蒽 - 烯量替代列。