Methods for producing gallium and other oxo/hydroxo-bridged metal aquo clusters

Abstract

Metallic clusters can be produced by contacting a metal salt such as a metal nitrate with an organic reducing agent. Metals can be selected from a group consisting of metals exhibiting octahedral coordination, and nitrates of the selected metal or metals are contacted with, for example nitrosobenzene. Binary, tertiary, or other clusters can be produced.

1 . A method of producing a material, comprising: 
 providing a metal nitrate, wherein the metal is selected from a group consisting of metals exhibiting octahedral coordination geometry; and    contacting the metal reagent with an effective amount of an organic reducing agent to produce the material.    
   
   
       2 . The method of  claim 1 , wherein the organic reducing agent has a formula R—NO, wherein R is aliphatic, aromatic, or heteroaromatic.  
   
   
       3 . The method of  claim 1 , wherein the metal is selected from a group consisting of Al, Mn, Fe, Ga, In, Ni, Fe, Ge, Eu, Th, or Sm.  
   
   
       4 . The method of  claim 1 , further comprising contacting the metal reagent and the organic reducing agent in a solvent, wherein the metal reagent and the organic reducing agent are soluble in the solvent, and the organic reducing agent is nitrosobenzene.  
   
   
       5 . The method of  claim 4 , wherein the solvent is an alcohol.  
   
   
       6 . The method of  claim 5 , wherein the solvent consists essentially of methanol.  
   
   
       7 . The method of  claim 4 , further comprising evaporating the solvent to obtain crystals of the material.  
   
   
       8 . The method of  claim 1 , further comprising providing a nitrate of a first metal and a nitrate of a second metal different from the first metal, wherein the first metal and the second metal are selected from the group of metals exhibiting octahedral coordination, and contacting the first metal nitrate and the second metal nitrate with the organic reducing agent.  
   
   
       9 . The method of  claim 8 , wherein the material has a formula [M A N B7 (μ 3 -OH) 6 (μ-OH) 18 (H 2 O) 24 ](NO 3 ) 15 , M and N represent the first metal and the second metal, respectively, and A and B are integers greater than or equal to zero such that A+B=13, and μ 3  denotes a number of OH groups bridging three atoms of M or N, and μ denotes a number of OH groups bridging two atoms of M or N.  
   
   
       10 . The method of  claim 9 , wherein the material has a formula [Ga 7 In 6 (μ 3 -OH) 6 (μ-OH) 18 (H 2 O) 24 ](NO 3 ) 15 .  
   
   
       11 . The method of  claim 1 , wherein the material is a cluster having a formula [M 13 (μ 3 -OH) 6 (μ-OH) 18 (H 2 O) 24 ](NO 3 ) 15 , wherein M is the metal selected from a group consisting of metals exhibiting octahedral coordination geometry, μ 3  denotes a number of OH groups bridging three atoms of M, and μ denotes a number of OH groups bridging two atoms of M.  
   
   
       12 . The method of  claim 11 , wherein M is selected from the group consisting of Al, Mn, Fe, Ga, In, Ni, Fe, Ge, Eu, Th, and Sm.  
   
   
       13 . The method of  claim 12 , wherein M is Ga or Al.  
   
   
       14 . The method of  claim 1 , wherein the organic reducing agent is selected from a group consisting of phosphines and sulfoxides.  
   
   
       15 . A composition, having a formula [Ga 13 (μ 3 -OH) 6 (μ-OH) 18 (H 2 O) 24 ](NO 3 ) 15 , wherein μ 3  denotes a number of OH groups bridging three atoms of Ga, and μ denotes a number of OH groups bridging two atoms of Ga.  
   
   
       16 . A composition, having a formula [Ga 7 In 6 (μ 3 -OH) 6 (μ-OH) 18 (H 2 O) 24 ](NO 3 ) 15 , wherein μ 3  denotes a number of OH groups bridging three atoms of Ga or In, and μ denotes a number of OH groups bridging two atoms of Ga or In.  
   
   
       17 . A method of producing a material, comprising: 
 providing a first metallic reagent having a formula [M 13 (μ 3 -OH) 6 (μ-OH) 18 (H 2 O) 24 ](NO 3 ) 15 , wherein M is a metal is selected from a group consisting of metals exhibiting octahedral coordination geometry, μ 3  denotes a number of OH groups bridging three atoms of Ga, and μ denotes a number of OH groups bridging two atoms of Ga; and    contacting the first metallic reagent with an effective amount of an organic reducing agent to produce the material.    
   
   
       18 . The method of  claim 17 , wherein the organic reducing agent has a formula R—NO, wherein R is aliphatic, aromatic, or heteroaromatic to produce the material.  
   
   
       19 . The method of  claim 17 , where the metal M is selected from the group consisting of Ga, Al, and In.  
   
   
       20 . The method of  claim 17 , further comprising contacting the first metallic reagent with the organic reducing agent in a basis solution.  
   
   
       21 . The method of  claim 17 , wherein the organic reducing agent has a formula R—NO, wherein R is aliphatic, aromatic, or heteroaromatic to produce the material.  
   
   
       22 . The method of  claim 21 , wherein the organic reducing agent is nitrosobenzene.  
   
   
       23 . A method of making a bridged metal cluster, comprising: 
 providing a reagent having a formula A x B y , wherein A is a metal selected from a group of metals exhibiting octahedral coordination geometry, B is an oxyanion, and x and y are integers between 0 and 10; and    contacting the reagent with an organic reducing agent.    
   
   
       24 . The method of  claim 24 , wherein the metal is selected from the group consisting Al, Mn, Fe, Ga, In, Ni, Fe, Ge, Eu, Th, or Sm, and B is an oxyanion selected from a group consisting of nitrate, sulfate, carbonate, and phosphate.  
   
   
       25 . The method of  claim 25 , wherein the organic reducing agent is selected from a group consisting of nitroso compounds and nitroamines.