Vapochromic coordination polymers for use in analyte detection

Abstract

Vapochromic coordination polymers useful for analyte detection are provided. The vapochromism may be observed by visible color changes, changes in luminescence, and/or spectroscopic changes in the infrared (IR) signature. One or more of the above chromatic changes may be relied upon to identify a specific analyte, such as a volatile organic compound or a gas. The chromatic changes may be reversible to allow for successive analysis of different analytes. The polymer has the general formula M W [M′ X (Z) Y ] N wherein M and M′ are the same or different metals capable of forming a coordinate complex with the Z moiety; Z is selected from the group consisting of halides, pseudohalides, thiolates, alkoxides and amides; W is between 1-6; X and Y are between 1-9; and N is between 1-5. One embodiment provides [Metal(CN) 2 ]-based coordination polymers with vapochromic properties, such as Cu[Au(CN) 2 ] 2 and Zn[Au(CN) 2 ] 2 polymers.

1 . A vapochromic polymer comprising:
   M W [M′ X (Z) Y ] N  
   wherein M and M′ are the same or different metals capable of forming a coordinate complex with the Z moiety;   Z is selected from the group consisting of halides, pseudohalides, thiolates, alkoxides and amides;   W is between 1-6;   X and Y between 1-9; and   N is between 1-5.   
     
     
         2 . The polymer as defined in  claim 1 , wherein W and X are 1, Y is 2, and N is 2 or 3. 
     
     
         3 . The polymer as defined in  claim 2 , wherein said polymer is reversibly vapochromic. 
     
     
         4 . The polymer as defined in  claim 1 , wherein M is a transition metal. 
     
     
         5 . The polymer as defined in  claim 1 , wherein M′ is a metal selected from the group consisting of Au, Ag, Hg and Cu. 
     
     
         6 . The polymer as defined in  claim 1 , wherein Z is a pseudohalide selected from the group consisting of CN, SCN, SeCN, TeCN, OCN, CNO and NNN. 
     
     
         7 . The polymer as defined in  claim 1 , wherein M is selected from the group consisting of Cu, Zn, Sc, Ti, V, Cr, Mn, Fe, Co and a lanthanide. 
     
     
         8 . The polymer as defined in  claim 7 , wherein M is Cu or Zn. 
     
     
         9 . The polymer as defined in  claim 1 , wherein M′ is selected from the group consisting of Au and Ag and wherein Z is CN. 
     
     
         10 . The polymer as defined in  claim 9 , wherein M′ is Au and wherein X is 1 and Y is 2. 
     
     
         11 . The polymer as defined in  claim 1 , further comprising an organic ligand bound to M. 
     
     
         12 . The polymer as defined in  claim 11 , wherein said organic ligand comprises at least one nitrogen, oxygen, sulphur or phosphorus donor. 
     
     
         13 . The polymer as defined in  claim 1 , further comprising a counterbalancing cation or anion. 
     
     
         14 . The polymer as defined in  claim 1 , wherein said polymer is vapoluminescent. 
     
     
         15 . The polymer as defined in  claim 1 , wherein X=1 and Y=2. 
     
     
         16 . A composition comprising a polymer as defined in  claim 1 , and an analyte adsorbed to said polymer. 
     
     
         17 . The composition as defined in  claim 16 , wherein said analyte is a volatile organic compound. 
     
     
         18 . The composition as defined in  claim 16 , wherein said analyte is a gas having a donor hydrogen, nitrogen, oxygen, sulphur or phosphorus atom. 
     
     
         19 . A solid-state vapochromic structure comprising a polymer as defined in  claim 1 . 
     
     
         20 . A solid-state vapochromic structure comprising a composition as defined in  claim 16 . 
     
     
         21 . The use of a structure a defined in  claim 19  for vapochromically sensing the presence of an analyte. 
     
     
         22 . An analyte-bound complex comprising an analyte adsorbed to a polymer as defined in  claim 1 . 
     
     
         23 . A method of detecting an analyte comprising:
 (a) providing a polymer as defined in  claim 1 ;   (b) exposing said polymer to a supply of said analyte; and   (c) detecting any chromatic changes in said polymer resulting from exposure to said analyte.   
     
     
         24 . The method as defined in  claim 23 , wherein said detecting comprises sensing any changes in the colour of said polymer. 
     
     
         25 . The method as defined in  claim 23 , wherein said detecting comprises sensing any changes in the luminescence of said polymer. 
     
     
         26 . The method as defined in  claim 23 , wherein said detecting comprises spectroscopically identifying any changes in the infrared signature of said polymer. 
     
     
         27 . The method as defined in  claim 26 , wherein said spectroscopically identifying comprises detecting the number and position of ν CN  spectroscopic bands. 
     
     
         28 . The method as defined in  claim 23 , wherein said chromatic changes are reversible. 
     
     
         29 . The method as defined in  claim 28 , wherein said supply comprises different analytes and wherein steps (b) and (c) are dynamically repeated in respect of successive ones of said analytes. 
     
     
         30 . The method as defined in  claim 23 , wherein M is Cu or Zn and wherein M′ is Au. 
     
     
         31 . The method as defined in  claim 30 , wherein said polymer is selected from the group consisting of Cu[Au(CN) 2 ] 2  and Zn[Au(CN) 2 ] 2 . 
     
     
         32 . The method as defined in  claim 23 , wherein said analyte is a volatile organic compound. 
     
     
         33 . The method as defined in  claim 23 , wherein said analyte is a gas. 
     
     
         34 . The method as defined in  claim 29 , wherein said gas is CO and CO 2 . 
     
     
         35 . The use of a polymer as defined in  claim 1  for vapochromically sensing the presence of an analyte. 
     
     
         36 . A method of synthesizing a polymer as defined in  claim 8  comprising reacting a Cu(II) or a Zn(II) salt with [Au(CN) 2 ] −  in a solvent. 
     
     
         37 . A vapochromic composition comprising a metal complex represented by the general formula M W [M′ X (Z) Y ] N  
 wherein M and M′ are the same or different metals capable of forming a coordinate complex with the Z moiety; 
 Z is selected from the group consisting of halides, pseudohalides, thiolates, alkoxides and amides; 
 W is between 1-6; 
 X and Y between 1-9; and 
 N is between 1-5. 
 
     
     
         38 . The composition as defined in  claim 37  wherein;
 M is selected from the group consisting of Cu and Zn; 
 M′ is selected from the group consisting of Au, Ag, Hg and Cu; 
 Z is a pseudohalide selected from the selected from the group consisting of CN, SCN, SeCN, TeCN, OCN, CNO and NNN; 
 W and X are 1; 
 Y is 1; and 
 N is 2 or 3. 
 
     
     
         39 . The method as defined in  claim 23 , wherein said analyte is selected from the group consisting of ammonia and amines. 
     
     
         40 . The method as defined in  claim 39 , wherein said analyte is ammonia. 
     
     
         41 . The method as defined in  claim 39 , wherein said polymer comprises Zn[Au(CN) 2 ] 2  in any of its polymorphic forms. 
     
     
         42 . The method as defined in  claim 39 , wherein said polymer comprises Cu[Au(CN) 2 ] 2 . 
     
     
         43 . The method as defined in  claim 39 , wherein M is Cu or Zn, M′ is Au, Z is CN, W is 1 and X and Y is 2. 
     
     
         44 . The method as defined in  claim 39 , wherein said detecting comprises sensing any changes in luminescence of said polymer. 
     
     
         45 . The method as defined in  claim 39 , wherein said detecting comprises sensing any changes in colour of said polymer. 
     
     
         46 . The method as defined in  claim 39 , wherein said detecting comprises spectroscopically identifying any changes in the infrared signature of said polymer. 
     
     
         47 . The method as defined in  claim 40 , wherein said exposing comprises exposing said polymer to ammonia present in the breath of a patient. 
     
     
         48 . The method ad defined in  claim 41 , wherein said polymer comprises Zn[Au(CN) 2 ] 2  in its β polymorphic form.