The reaction of aqueous solutions of
K2PdCl4 and
K3Co(CN)6 results in gellike
polymeric
materials, characterized by bridging cyanides between the central
metals of the adducts.
These materials tend to be rigid in nature but contain in excess
of 95% water by weight.
We refer to these novel transition metal based hydrogels as
cyanogels. In contrast to classic
inorganic hydrogels these materials are not based on an oxide network.
Dehydration of the
cyanogels results in amorphous xerogels which maintain the initial
polymeric structure of
the cyanogel. Thermal processing of gels containing palladium and
cobalt centers under an
inert atmosphere at temperatures between 200 and 500 °C, produces a
new metastable
material. Sintering between 500 and 1000 °C produces
ferromagnetic alloys, while processing
under oxygen in the same temperature region gives the ceramic mixed
oxide material PbCoO2,
having the delafossite structure.
Adenosine 5'-diphosphoribose (ADPR) and a second compound, which may be nicotinamide, are the newly discovered photoproducts resulting from irradiation of beta-nicotinamide adenine dinucleotide (beta-NADH) in the wavelength range of 300-400 nm under oxygen-poor conditions. Both products emerge there even exclusively, whereas, at higher oxygen concentrations, the oxidized form of nicotinamide adenine dinucleotide (NAD+) is additionally formed, although still as a minor product. The development of ADPR and NAD+ is clearly oxygen-dependent, while, for the formation of the second photoproduct, small quantities of oxygen appear to be sufficient.
The reaction of aqueous solutions of SnCl 4 ‚5H 2 O and K 4 Fe(CN) 6 in a 2/1 Sn/Fe atomic ratio results in a hydrogelled polymeric material, characterized by bridging cyanides between the central metals of the adducts. Materials of this type have previously been noted upon reaction of PdCl 4 2with cyanometalates in aqueous solution and have been referred to as cyanogels. Dehydration of Sn/Fe cyanogels results in xerogels that maintain the initial polymeric structure of the hydrogel. Thermal processing of such gels under an air atmosphere at 900 °C produces a solid homogeneous mixture of microcrystalline SnO 2 and Fe 2 O 3 .
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.
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