Assembly And Properties Of Molecular Coordination Containers Incorporating Sulfonylcalix[4] Arene

The molecular coordination containers,constructed via metal coordination bonds,possess well-defined cavities,that provide a restricted chemical microenvironment for guest encapsulation giving rise to various applications,such as transportation of small molecules,gas storage and separation,sensing,catalysis and molecular recognition.The functionalization is a powerful strategy to improve or modify the properties and applications of molecular coordination containers.In this dissertation,we focus on the development of functionalized coordination containers based on sulfonylcalix[4]arene,which gives rise to the unique properties of proton sensing,guest recognition,gas separation,and LB film fabraction.The results of this dissertation are shown below.1.Proton-recognition and fluorescent sensing properties of synthetic dual-functionalized coordination containersWe designed a 1,3-benzenedicarboxylate(1,3-BDC)derivative(L1)imbedded with a secondary amine(-NHR)group serving as the principal H+binding site and a pyrene unit serving as the fluorescent tag,which formed the barrel-shaped coordination containers(1-Zn and 1-Co)upon reacting with p-tert-butylsulfonylcalix[4]arene(TBSC)and divalent metal ions.Molecular containers 1-Zn and 1-Co exhibit proton-dependent fluorescent switching behavior,which involves a two-step mechanism pertaining to proton binding by both amino and pyrenyl moieties of the container constructs.The remarkable proton binding capacity,combined with the ease of switching on and off the fluorescent emission of the supramolecular sensors via small-molecule "modulators",opens exiting opportunities for proton sensing and manipulation in both chemistry and biology.2.Engineering solid-state porosity of synthetic coordination containers via modification of exo-cavitiesTwo new coordination containers(named as 2-Co and 2-Ni)have been successfully isolated from the self-assembly reactions of the container precursor p-phenylsulfonylcalix[4]arene,Ni(Ⅱ)or Co(Ⅱ)ion,and diphenylmethane-4,4’-dicarboxylic acid.Crystal structure analysis revealed that these two coordination supercontainers possess a similar endo cavity and two deeper exo cavities compared to the related coordination containers based on p-tert-butylsulfonylcalix[4]arene.Gas and vapor adsorption studies indicated that the new compounds are permanently porous and show much better CO2/O2 and CO2/N2 selectivity and higher vapor adsorption than the tert-butyl analogues.3.The Fabrication of LB Films based on square barrel-shaped coordination containersThe chloroform-soluble coordination containers,which assembled from Co2+,p-tert-butylsulfonylcalix[4]arene and 1,3-benzenedicarboxylate(1,3-BDC)derivatives bearing different hydrophobic/hydrophilic groups,were dispersed onto the air-water interfaces and investigated by the Langmuir-Blodgett technique.The surface pressure-molecular area(π-A)isotherms indicated that the hydrophilic modification on the organic linkers can lead to a closer molecular packing on the air-water interphase.