Acridinylresorcinol as a self-complementary building block of robust hydrogen-bonded 2D nets with coordinative saturation. Preservation of crystal structures upon guest alteration, guest removal, and host modification.
Acridinylresorcinol as a self-complementary building block of robust hydrogen-bonded 2D nets with coordinative saturation. Preservation of crystal structures upon guest alteration, guest removal, and host modification.
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DOI：
10.1021/ja026704l
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发表时间：
2002-09
影响因子：
15
通讯作者：
Toshihiro Tanaka;Takashi Tasaki;Y. Aoyama
中科院分区：
文献类型：
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作者：
Toshihiro Tanaka;Takashi Tasaki;Y. Aoyama
吖啶基间二酚宿主3（9-（3,5-二羟基-1-苯基）吖啶）形成类似3的加合物。(苯),3。（氯仿），3.0.5（甲苯），3。(异丁基苯甲酸酯)。修饰后的吖啶醇宿主4（9-（3,5-二羟基-1-苯基）-4-羟基吖啶）在吖啶环上有一个额外的羟基，可以得到4这样的加合物。(苯),4。（氯仿），4.0.5（甲苯），0.5（水），4.（甲醇）。（水），4。(乙酸乙酯)。在晶体中，宿主3和宿主4形成氢键（O-H…O-H）聚间苯二酚链，通过O-H…N氢键生成配位饱和的(O-H…O-H…N)二维网由双氢键和反平行堆叠，自互补的环状二聚体3(2)或4(2)作为刚性构建块组成，其他柔性的O-H…O-H氢键因此形成环番状结构。这个网络在上述加合物中被证明保存得非常好。客体分子，在许多情况下是无序的，被合并到留下的空腔中。小的极性客体与宿主4的结合主要是由于与吖啶环上的羟基形成氢键。因此，后者仅作为保存腔的极性调节剂。加合物3。（苯），即3(2)。2（苯）很容易失去在每个空腔中结合的两个客体分子中的一个，从而形成半填充的微孔加合物3(2)。通过x射线粉末衍射和可逆的langmuir型吸附/解吸等温线证实，吸附1 mol苯再生起始全加合物而不发生相变。讨论了设计刚性晶体结构的自互补策略，并特别提到了晶体工程中系统摄动/变分方法的可能性。
Acridinylresorcinol host 3 (9-(3,5-dihydroxy-1-phenyl)acridine) forms such adducts as 3.(benzene), 3.(chloroform), 3.0.5(toluene), and 3.(isobutyl benzoate). Modified acridinol host 4 (9-(3,5-dihydroxy-1-phenyl)-4-hydroxyacridine) having an additional OH group on the acridine ring affords such adducts as 4.(benzene), 4.(chloroform), 4.0.5(toluene).0.5(water), 4.(methanol).(water), and 4.(ethyl acetate). In the crystals, hosts 3 and 4 form hydrogen-bonded (O-H...O-H) poly(resorcinol) chains which are linked together via interchain O-H...N hydrogen bonds to give a coordinatively saturated (O-H...O-H...N) 2D net composed of doubly hydrogen-bonded and antiparallel-stacked, self-complementary cyclic dimer 3(2) or 4(2) as a rigidified building block, the otherwise flexible O-H...O-H hydrogen bonds being thereby taken in a cyclophane-like structure. This network turns out to be remarkably well preserved among the above adducts. Guest molecules, which are disordered in many cases, are incorporated in the cavities left. The binding of small polar guests to host 4 is primarily due to hydrogen bonding to the OH group on the acridine ring. The latter therefore acts only as a polarity modifier of preserved cavities. Adduct 3.(benzene), that is, 3(2).2(benzene) readily loses one of two guest molecules bound in each cavity to give a microporous half-filled adduct 3(2).(benzene) which adsorbs 1 mol of benzene to regenerate the starting full adduct without involving a phase change, as confirmed by X-ray powder diffractions and reversible Langmuir-type adsorption/desorption isotherms. The self-complementarity strategy for designing rigid crystal structures is discussed with a particular reference to the possibility of systematic perturbation/variation approaches in crystal engineering.