Organometallic Derivatives of Cyclotriphosphazene as Precursors of Nanostructured Metallic Materials: A New Solid State Method |
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Authors: | Carlos Díaz María Luisa Valenzuela Luis Zúñiga Colm O’Dwyer |
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Affiliation: | 1. Departamento de Química, Facultad de Ciencias, Universidad de Chile, Las Palmeras, 3425, Santiago, Chile 2. Department of Physics and Materials & Surface Science Institute, University of Limerick, Limerick, Ireland
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Abstract: | The cyclic phosphazene trimers N3P3(OC6H5)5OC5H4N·Ti(Cp)2Cl]PF6] (3), N3P3(OC6H4CH2CN·Ti(Cp)2Cl)6]PF6]6 (4), N3P3(OC6H4-But)5(OC6H4CH2CN·Ti(Cp)2Cl)]PF6] (5), N3P3(OC6H5)5C6H4CH2CN·Ru(Cp)(PPh3)2]PF6] (6), N3P3(OC6H5)5C6H4CH2CN·Fe(Cp)(dppe)]PF6] (7) and N3P3(OC6H5)5OC5H4N·W(CO)5 (8) were prepared and characterized. As a model, the simple compounds HOC5H5N·Ti(Cp)2Cl]PF6 (1) and HOC6H4CH2CN·Ti(Cp)2Cl]PF6 (2) were also prepared and characterized. Pyrolysis of the organometallic cyclic trimers in air yields metallic nanostructured
materials, which according to transmission and scanning electron microscopy (TEM/SEM), energy-dispersive X-ray microanalysis
(EDX), and IR data, can be formulated as either a metal oxide, metal pyrophosphate or a mixture in some cases, depending on
the nature and quantity of the metal, characteristics of the organic spacer and the auxiliary substituent attached to the
phosphorus cycle. Atomic force microscopy (AFM) data indicate the formation of small island and striate nanostructures. A
plausible formation mechanism which involves the formation of a cyclomatrix is proposed, and the pyrolysis of the organometallic
cyclic phosphazene polymer as a new and general method for obtaining metallic nanostructured materials is discussed. |
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