Modular assembly of metal-organic super-containers incorporating calixarenes

Abstract

A new strategy to design container molecules is presented. Sulfonylcalix[4]arenes, which are synthetic macrocyclic containers, are used as building blocks that are combined with various metal ions and tricarboxylate ligands to construct metal-organic ‘super-containers’ (MOSCs). These MOSCs possess both endo and exo cavities and thus mimic the structure of viruses. The synthesis of MOSCs is highly modular, robust, and predictable.

We claim: 
     
         1 . A super-container molecule, comprising at least one metal-organic container molecule further comprising:
 a. sulfonylcalix[4]arenes;   b. at least one metal ion;   c. an organic ligand;   d. at least one internal cavity; and   e. at least one external cavity,   wherein the sulfonylcalix[4]arenes are linked by the at least one metal ion, and   wherein the organic ligand is a linker selected from the group consisting of 1,3,5-benzenetricarboxylate, 1,4-benzenedicarboxylate, 1,3-benzenedicarboxylate, and 4,4′-methylenedibenzoate.   
     
     
         2 . The super-container of  claim 1 , wherein the metal-organic container molecule comprises at least four metal ions. 
     
     
         3 . The super-container of  claim 1 , wherein the at least one metal ion is selected from the group consisting of divalent cations of transition metals and alkaline earth metals. 
     
     
         4 . The super-container of  claim 1 , wherein the at least one metal ion is selected from the group consisting of cobalt, magnesium, manganese, and nickel. 
     
     
         5 . The super-container of  claim 1 , further comprising an endo cavity. 
     
     
         6 . The super-container of  claim 1 , wherein the linker comprises an exo binding domain. 
     
     
         7 . A metal-organic super-container molecule, comprising:
 a. at least one internal cavity;   b. at least one external cavity; and   c. sulfonylcalix[4]arenes linked by metal ions and an organic linker;   wherein the organic linker is a dicarboxylate linker having an edge-directed octahedral shape or a barrel shape; further wherein the dicarboxylate linker is 1,4-benzenedicarboxylate or 1,3-benzenedicarboxylate.   
     
     
         8 . The metal-organic super-container molecule of  claim 7 , wherein the internal cavity further comprises a first internal cavity size, and the external cavity has a first external cavity size, and the first internal cavity size is increased by the dicarboxylate linker to a second, larger internal cavity size. 
     
     
         9 . The metal-organic super-container molecule of  claim 7 , wherein the metal ions are selected from the group consisting of: cobalt, magnesium, manganese, and nickel. 
     
     
         10 . The metal-organic super-container molecule of  claim 7 , wherein the structure of the container molecule is capable of being adjusted by substituting one or more of the sulfonylcalix[4]arenes, metal ions, or organic ligands. 
     
     
         11 . The metal-organic super-container molecule of  claim 7 , wherein the molecule is capable of being adjusted to increase the size of the at least one internal cavity and at least one external cavity by substituting an expanded organic ligand. 
     
     
         12 . A metal-organic super-container molecule, comprising:
 a. at least one internal cavity;   b. at least one external cavity;   c. a sulfonylcalix[4]arenes;   d. at least one metal ion; and   e. an aromatic dicarboxylate organic linker,   wherein the aromatic dicarboxylate organic linker is selected from a group consisting of a linear-planar linker and an angular-planar linker.   
     
     
         13 . The super-container of  claim 12 , wherein the super-container is formed by substituting the aromatic dicarboxylate organic linker for a mono-carboxylate organic ligand. 
     
     
         14 . A super-container as defined in  claim 12 , wherein the functionality is selected from the group consisting of adsorptivity, porosity and solubility. 
     
     
         15 . A super-container of  claim 14 , wherein the functionality is adsorbing a contaminant material from a liquid. 
     
     
         16 . The super-container of  claim 12 , wherein the metal ions are selected from the group consisting of: cobalt, magnesium, manganese and nickel. 
     
     
         17 . The super-container of  claim 12 , wherein the dicarboxylate organic linker is an angular-planar aromatic carboxylate linker. 
     
     
         18 . The super-container of  claim 17 , wherein the angular-planar aromatic carboxylate linker is 1,3-benzenedicarboxylate. 
     
     
         19 . The super-container of  claim 12 , wherein the dicarboxylate organic linker is a linear-planar aromatic carboxylate linker. 
     
     
         20 . The super-container of  claim 19 , wherein the linear-planar aromatic carboxylate linker is 1,4-benzenedicarboxylate.