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

研究表明，一种并苯双间苯二酚衍生物1形成了由氢键聚间苯二酚链和大空腔组成的分子片，这些空腔被蒽环覆盖和覆盖。这些空腔选择性地结合了各种客体分子。(1)由微孔晶体1催化的Diels-Alder反应如前所述，晶体1在每个空腔中含有两个乙酸乙酯和苯分子。当客体分子分别转变为丙烯醛(双烯体)和1.3-环己二烯时，一个简单的催化Diels-Alder反应以高度立体选择性(内选择性)的方式发生，其中1作为微孔催化剂的作用是(A)在空腔中组装两个反应物，(2)通过主客体氢键通过酸催化激活双烯体，(3)在三维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Chainsracene单间苯二酚化合物2的功能自组装形成了类似的一维氢键网络。链通过插入正交菲取代基连接在一起；在空腔中客体分子以1：1的主-客体化学计量比包含在一起。与主体1的2D网络中的空穴相比，空穴的厚度要小得多，并且在客体结合中显示出新的厚度选择性，其中观察到直链烷基比支链烷基具有显著的偏好。用这种方法可以构建紧密堆积的蒽-客体交替柱。

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.