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Novel Inorganic Hydrogels Based on The Polymerization of Cyanometalate Transition Metal Complexes With [PdCl4]2-: A New Approach To Ceramic And Alloy Precursors

Published online by Cambridge University Press:  21 February 2011

Andrew B. Bocarsly ,
Gireesh Kumar  and
Marija Heibel
Andrew B. Bocarsly
Affiliation:
Department of Chemistry, Princeton University, Princeton, NJ 08550
Gireesh Kumar
Affiliation:
Department of Chemistry, Princeton University, Princeton, NJ 08550
Marija Heibel
Affiliation:
Department of Chemistry, Princeton University, Princeton, NJ 08550
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Abstract

The reaction of a wide variety of cyanometalate complexes of the general form [M(CN)x]n- (where M= a transition metal ion) with square planar [PdCl4]2- in aqueous solution leads to the formation of linear polymers. Polymerization occurs via substitution of chloride ligands on the Pd(II) centers, by the nitrogen end of the cyanide ligand to generate extended bridging cyanide structures. Upon generation at room temperature polymer solutions of this type under go a sol-gel transition to generate robust hydrogels having water content in excess of 95%. In the case of the cyanocobaltate/tetrachloropalladate gel, pyrolysis at 900°C produces ferromagnetic Pd/Co metallic alloys having novel morphological character. Materials formed with a hydrogel having a 2:1 Pd to Co stoichiometry are found to be “sponge-like”. When placed in water, the metallic matrix swells becoming pliable and holding up to seven equivalents of water per metal site. The conductivity and magnetic properties of this material are maintained in the swollen state. Sintering of the Pd/Co hydrogel in air generates the layered oxide, PbCoO2 having a delafossite structure.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 346: Symposium N – Better Ceramics Through Chemistry VI , 1994 , 89
Copyright
Copyright © Materials Research Society 1998

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References

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