Hierarchical nanoporous diamondoid superstructure

Abstract

Disclosed herein are compositions, supramolecular assemblies, crystalline compositions, and methods of making and using the same. The composition comprises an organic ion and a counterion, wherein the organic ion comprises a molecular hub and arms extending therefrom and wherein the organic ion is capable of adopting a tripodal confirmation.

1 - 20 . (canceled) 
     
     
         21 . A composition comprising an organic ion and a counterion, wherein the organic ion comprises a molecular hub and arms extending therefrom and wherein the organic ion is capable of adopting a tripodal confirmation. 
     
     
         22 . The composition of  claim 21 , wherein the organic ion is hexacationic. 
     
     
         23 . The composition of  claim 21 , wherein the counterion is PF 6   −  or AsF 6   − . 
     
     
         24 . The composition of  claim 21 , wherein the organic ion is hexakis[(4,4′-bipyridin-1-ium)methylene]benzene. 
     
     
         25 . The composition of  claim 21 , wherein the organic ion is hexacationic hexakis[(4,4′-bipyridin-1-ium)methylene]benzene and the counter ion is PF 6   −  or AsF 6   − . 
     
     
         26 . A supramolecular assembly comprising the composition of  claim 21 , wherein four organic ions form a truncated tetrahedral subunit. 
     
     
         27 . The supramolecular assembly of  claim 26 , wherein the counterion is positioned within a cavity formed by the organic ion in a tripodal confirmation. 
     
     
         28 . The supramolecular assembly of  claim 26 , wherein the organic ion has D 3d  symmetry. 
     
     
         29 . The supramolecular assembly of  claim 26 , wherein the arms of adjacent organic ions are aligned anti-parallel. 
     
     
         30 . The supramolecular assembly of  claim 26 , wherein ten truncated tetrahedral subunits form a diamondoid unit. 
     
     
         31 . The supramolecular assembly of  claim 30 , the diamondoid unit forms a pore. 
     
     
         32 . A crystalline composition comprising composition of  claim 21  in the cubic, F d 3 space group. 
     
     
         33 . The crystalline composition of  claim 32 , wherein the crystalline composition is porous. 
     
     
         34 . The crystalline composition of  claim 32 , wherein crystalline composition has a unit cell comprising 16 organic ions. 
     
     
         35 . A method of preparing a supramolecular assembly or a crystalline composition, the method comprising precipitating a solution comprising the composition of  claim 21 . 
     
     
         36 . The method of  claim 35 , wherein the solution is precipitated by mixing the solution with an anti-solvent or wherein the solution is precipitated by slow vapor diffusion of an anti-solvent. 
     
     
         37 . A method for sequestering an ionic contaminant, the method comprising contacting a supramolecular assembly or a crystalline composition with the ionic contaminant, wherein the supramolecular assembly or crystalline composition comprises the composition of  claim 21 . 
     
     
         38 . The method of  claim 37 , wherein the contacting step exchanges at least a portion of the counterion within the supramolecular assembly or crystalline composition with the ionic contaminant. 
     
     
         39 . The method of  claim 38 , wherein the ionic contaminant is an oxoanion. 
     
     
         40 . The method of  claim 37  further comprising regenerating the supramolecular assembly or the crystalline composition. 
     
     
         41 . The method of  claim 35  further comprising replacing at least a portion of the counterion with a second counterion.