Supramolecular Structures Based on Bis(2-hydroxy-5-chlorophenyl) Sulfide and Spirobicromane with Bipyridines

Six new supramolecular structures have been prepared by bis(2-hydroxy-5-chlorophenyl) sulfide (HCS)
and/or spirobicromane (SBC) with bipyridine bases 4,4‘-bipyridyl (bipy), 1,2-di(4-pyridyl)ethylene (dipy-ete), 1,2-bis(4-pyridyl)ethane (bipy-eta), and 4,4‘-dipyridyl N,N‘-dioxide (dipy-dox). These molecular complexes are (HCS)·(bipy) 1, (HCS)·(dipy-ete) 2, (HCS)·(bipy-eta) 3, (HCS)·(dipy-dox) 4, (SBC)·(dipy-ete) 5, and (SBC)·(dipy-dox)·H2O 6,
respectively. The crystal structures of 1−6 have been determined by single crystal X-ray diffraction. All of these
molecular complexes exhibit supramolecular structures via O−H···N or O−H···O hydrogen bondings. Both 1 and 2
form interestingly [2 + 2] macrocyclic structures, whose sizes are ca. 12.495(6) Å × 5.087(6) Å and 14.774(6) Å ×
5.300(6) Å, respectively. Compounds 3 and 5 form one-dimensional zigzag chain structures. Compounds 4 and 6
form two-dimensional double helices. These results demonstrate that by changing the guest molecule, we can obtain
different hydrogen-bonded supramolecular structures through different interactions.

本研究通过双(2-羟基-5-氯苯基)硫醚(bis(2-hydroxy-5-chlorophenyl) sulfide, HCS)和/或螺双色满(spirobicromane, SBC)与联吡啶类配体4,4'-联吡啶(4,4‘-bipyridyl, bipy)、1,2-二(4-吡啶基)乙烯(1,2-di(4-pyridyl)ethylene, dipy-ete)、1,2-双(4-吡啶基)乙烷(1,2-bis(4-pyridyl)ethane, bipy-eta)以及4,4'-联吡啶-N,N'-二氧化物(4,4‘-dipyridyl N,N‘-dioxide, dipy-dox)进行超分子组装，成功制备得到6种新型超分子结构。对应的分子复合物依次为：(HCS)·(bipy) 1、(HCS)·(dipy-ete) 2、(HCS)·(bipy-eta) 3、(HCS)·(dipy-dox) 4、(SBC)·(dipy-ete) 5以及(SBC)·(dipy-dox)·H2O 6。
通过单晶X射线衍射(single crystal X-ray diffraction)解析了化合物1至6的晶体结构。所有上述分子复合物均通过O-H···N与O-H···O氢键构筑得到超分子结构。
其中，化合物1与2可形成别具特色的[2+2]大环结构，其尺寸分别约为12.495(6) Å × 5.087(6) Å与14.774(6) Å × 5.300(6) Å。化合物3与5呈现一维锯齿状链结构，化合物4与6则形成二维双螺旋结构。本研究结果表明，通过改变客体分子，可借助不同的相互作用得到各异的氢键型超分子结构。