分子间卤键和氢键控制的网络结构的组装

Intermolecular Halogen and Hydrogen Bonding-Controlled Self-Assembly of Network Structures

分别以四苯甲烷和四苯基卟啉为中心,端位引入四氟碘代苯,合成了两类四齿卤键供体分子,并合成了3,3’,5,5’-四甲基-4,4’-联吡啶(TMBP)作为卤键受体分子.以四苯甲烷为中心的卤键供体分子和TMBP基于分子间I…N卤键和H…N氢键在固相中自组装,得到一类超分子网络结构.晶体结构显示,一个四面体卤键供体分子通过两组I…N卤键和两组H…N氢键结合四个TMBP分子,与之对应,一个TMBP分子通过一组I…N卤键和一组H…N氢键结合两个四面体分子,形成单层网络结构,网格为宽度2.37nm的正方形结构,层与层之间通过其它氢键和卤键进一步堆积.卟啉类四齿卤键供体分子的晶体数据显示,通过较为复杂的分子间C—I…π及H…F等弱相互作用,供体分子自身进行平面组装,层与层之间通过π-π堆积等作用进一步堆积.

Two kinds of tetra-dentate halogen bonding donors were synthesized by introducing tetrafluoroiodide benzene into tetraphenylene methane and tetraphenyl porphyrin modules.3,3',5,5'-Tetramethyl-4,4'-bipyridine(TMBP)was synthesized as halogen bonding acceptor.A type of supramolecular network structure was constructed by self-assembly of tetraphenylmethane-centered halogen donor and TMBP in solid phase based on intermolecular I…N halogen bonds and H…N hydrogen bonds.The crystal structure shows that one tetrahedral halogen bonding donor binds four TMBP molecules through two sets of I…N halogen bonds and two sets of H…N hydrogen bonds,correspondingly,one TMBP molecule binds two tetrahedral molecules through one set of I…N halogen bonds and one set of H…N hydrogen bonds to form a monolayer network structure distributed with square structures with grid width of 2.37 nm.And further stacking is controlled by other hydrogen and halogen bonds between layers.The crystal data of tetradentate halogen bonding donor molecules of porphyrins show that donor molecules assemble themselves in plane controlled by more complex weak intermolecular C—I…πand H…F interaction,and further stacking is controlled byπ-πstacking between layers.