摘要
卤键是一种类似于氢键的具有方向性的非共价作用力。σ-hole理论是目前被广泛接受的能揭示卤键本质的理论,其合理性也在实验上被证明[1]。利用卤键构筑具有特定构型和功能性的超分子聚集体是其在晶体工程和材料科学领域得以应用的基础。N-alkyl ammonium resorcinarene halides(NARXs),一类衍生化的杯芳烃卤化物,在分子的上沿主体骨架通过环状的(…H-N-H…X~-…)_4(X=Cl,Br)多重氢键作用固定,不仅扩展了传统resorcinarene的空穴,而且赋予它进一步通过卤键延伸成二聚或多聚物的能力[2,3,4]。X-射线单晶衍射和NMR分析表明,NARXs能通过不同的卤键供体被构筑成Deep-Cavity-Cavitand、分子哑铃、二聚分子胶囊、多聚准分子胶囊、以及二聚单分子胶囊等具有特定构型的聚集体,同时相比于母体,其主客体性质也得到了改善。
Halogen bonding(XB) is a directional non-covalent interaction similar with hydrogen bonding(HB).σ-hole theory is the most accepted theory accounting for the nature of such interaction,which has been verified theoretically and experimentally.Construction of specific functional supramolecular assemblies from XBs is the foundation of its application in crystal engineering and material science.N-alky1 ammonium resorcinarene halides(NARXs) with the upper rim stabilized by cyclic(…H-N-H…X~-…)_4(X=C1,Br) HBs,have potential ability to be extended via additional HBs and XBs.X-ray crystallography and NMR analyses prove that in the presence of different XB donors,NARXs can be constructed to assemblies of deep-cavity-cavitand,dimeric molecular capsule,pseudo-polymeric molecular capsule,and dimeric single-molecular-capsule,which compared with the parent compounds,have better host-guest properties.
引文
[1]Cavallo,G.,Metrangolo,P.;Milani,R.;Pilati,T.;Priimagi,A.;Resnati,G.;Terraneo,G.Chem.Rev.2016,116:2478-2601.
[2]Beyeh,N.K.,Pan,F.;Rissanen,K.Cryst.Growth Des.2015,14:6161-6165.
[3]Beyeh,N.K.,Pan,F.;Rissanen,K.Angew.Chem.Int.Ed.2014,54:7303-7307.
[4]Pan,F.;Beyeh,N.K.;Rissanen,K.J.Am.Chem.Soc.2015,137:10406-10413.