Reversible metallopolymer network

Abstract

The invention provides a metallopolymer coordination network comprising one or more coinage or similar metals and in some embodiments, a glyme or glyme-equivalent. The composition has an amorphous polymer network that is significantly stronger than previously reported supramolecular hydrogels synthesized without glyme. Glyme chain length and water content strongly influence the mechanical, electronic, and optical behavior of the network.

What is claimed is: 
     
         1 . A metallopolymer coordination network composition comprising a metallopolymer of Formula I: 
       
         
           
           
               
               
           
         
       
       wherein
 M is a coinage metal selected from copper, gold, silver, tin, nickel, and aluminum; and 
 R—S is a sulfur-containing moiety; 
 
       wherein the metallopolymer is a polymer of coinage metal atoms linked together by the sulfur atoms of the sulfur-containing moieties, wherein one or more of the sulfur-containing moieties comprise carboxy or amino functional groups. 
     
     
         2 . The composition of  claim 1  further comprising water. 
     
     
         3 . The composition of  claim 1  wherein the composition is a reversible gel, wherein gel properties of the composition are restored after rehydration of the corresponding dehydrated gel. 
     
     
         4 . The composition of  claim 1  wherein each M is copper, gold, or silver. 
     
     
         5 . The composition of  claim 1  wherein each R—S moiety of Formula I is a sulfur-containing diacid, amino acid, dipeptide, tripeptide, oligopeptide, or polypeptide. 
     
     
         6 . The composition of  claim 5  wherein the sulfur-containing moiety linking the coinage metals comprises thiomalic acid, thioacetic acid, glutathione, or cysteine. 
     
     
         7 . The composition of  claim 1  wherein the composition is electrically or ionically conductive. 
     
     
         8 . The composition of  claim 1  comprising about 40 wt % to about 60 wt % water, wherein the composition is a fluid. 
     
     
         9 . The composition of  claim 1  comprising about 15 wt % to about 40 wt % water, wherein the composition is a gel. 
     
     
         10 . The composition of  claim 1  comprising about 0.1 wt % to about 15 wt % water, wherein the composition is a solid. 
     
     
         11 . The composition of  claim 1  wherein the metallopolymer of Formula I is represented by Formula IB: 
       
         
           
           
               
               
           
         
       
       wherein
 R—S is a sulfur-containing moiety wherein the ratio (R—S):M is 1:1; and 
 Formula I is coordinated to one or more compounds of Formula A: 
 
       
         
           
           
               
               
           
         
         wherein
 each A of Formula IB is a Formula A moiety coordinated to M of Formula IB; 
 X is O or NR′ wherein R′ is H, alkyl, or aryl; 
 R 1  and R 2  are each independently OH, alkoxy, or N(R a ) 2  wherein each R a  is independently H or (C 1 -C 8 )alkyl; and 
 n is 1, 2, 3, 4, or about 5 to about 50. 
 
       
     
     
         12 . A metallopolymer composition of Formula II: 
       
         
           
           
               
               
           
         
       
       wherein
 each M is a coinage metal selected from copper, gold, silver, tin, nickel, titanium; and 
 each R is a sulfur-containing moiety comprising a carboxy or amino functional group wherein its sulfur atom is linked to M of the metallopolymer of Formula II; 
 
       wherein the ratio of the sulfur containing moiety and M is about 1:1, the metallopolymer is a straight chain metallopolymer further comprising immobilized water, and the composition is electrically or ionically conductive. 
     
     
         13 . The composition of  claim 12  wherein the composition is a non-lamellar gel comprising about 15 wt % to about 40 wt % water. 
     
     
         14 . The composition of  claim 13  wherein each M is copper or gold, each R—S is thiomalic acid or cysteine, and the elasticity of the composition ranges from about 15 MPa to about 40 MPa. 
     
     
         15 . The composition of  claim 14  wherein the number of repeating M-S moieties is about 3 to about 50. 
     
     
         16 . A composition according to  claim 1  prepared by combining (a) an aqueous solution comprising a coinage metal salt and thiomalic acid, thioacetic acid, glutathione, or cysteine, and (b) a molar excess of glyme, or a molar excess of a nitrogen-glyme equivalent, in water, for a sufficient period of time to form a dense phase comprising the metallopolymer coordination network composition wherein the composition is a non-lamellar gel. 
     
     
         17 . A metallopolymer material comprising a plurality of nanoparticles, a base, and water;
 wherein each of the nanoparticles is comprised of a plurality of oligomer segments and each of the oligomer segments is comprised of a thiol and a metal; and wherein the oligomer segments are coordinated to adjacent oligomer segments.   
     
     
         18 . The metallopolymer material according to  claim 17  wherein each oligomer segment is an M-SR oligomer, wherein M is a coinage metal and R is an organic moiety comprising a carboxy or amino functional group. 
     
     
         19 . The composition of  claim 18  wherein each M is copper, gold, or silver. 
     
     
         20 . The composition of  claim 19  wherein R is thiomalic acid, thioacetic acid, glutathione, or cysteine. 
     
     
         21 . A method for forming a metallopolymer material:
 wherein the metallopolymer material comprises:
 a plurality of nanoparticles, a base, and water, 
 wherein each of the nanoparticles is comprised of a plurality of oligomer segments and each of the oligomer segments is comprised of a thiol and a metal; and wherein the oligomer segments are coordinated to adjacent oligomer segments; 
 the method comprising: 
 combining (a) an aqueous solution comprising a coinage metal salt, base, and thiomalic acid, thioacetic acid, glutathione, or cysteine, and (b) a molar excess of glyme, or a molar excess of a nitrogen-glyme equivalent, in a concentration of water, for a sufficient period of time to form a dense phase; and 
 equilibrating the concentration of water in the dense phase to form the metallopolymer material wherein the metallopolymer material is a non-lamellar gel.