Synthesis and Characterization of Sulfur-Containing Nongeminal Cyclic and Polymeric Alkylarylphosphazenes

Abstract

The methyl groups in both cyclic and polymeric methylphenylphosphazenes, [Me(Ph)PN]3 and [Me(Ph)PN]n, were modified using deprotonation-substitution and subsequent oxidation reactions to incorporate both thioether and sulfone functional groups. The new cyclic phosphazenes, cis-[Ph(RSCH2)-PN]3, 3 and 5, and cis-{Ph[RS(O)2CH2]PN}3, 6 and 7, where R ) Me or Ph, and the corresponding copolymers [Me(Ph)PN]x[Ph(RSCH2)PN]y, 8 and 9, and [Me(Ph)PN]x[{Ph[RS(O)2CH2]PN}y, 10 and 11, with varying ratios of x:y, were characterized by NMR and IR spectroscopy and thermal analysis.Crystallographic analysis of the cyclics 3 and 6 show that these molecules retain the basket shape of the nongeminal cis isomers with all the new functional groups opposite from the phenyl groups about the planar P3N3 ring. A cyclic trimer, cis-[Ph3(MeSCH2)2MeP3N3], 4, in which only two thioether groups had been incorporated was also isolated. The thioether-substituted polyphosphazenes, 8 and 9, were used as phase-transfer reagents and stabilizing hosts for the synthesis of gold nanoparticles. Analysis by UV spectroscopy and transmission electron microscopy indicated that the average gold particle size in these polymer nanocomposites was 3.2(0.9) nm. In solution, some aggregation of the nanoparticles was observed after one week, but the nanocomposites remain unchanged in the absence of solvent.

Metallocyclo‐ and Polyphosphazenes Containing Gold or Silver: Thermolytic Transformation into Nanostructured Materials

“…[6] Silver [7] and gold [8] derivatives of phosphazenes (cyclic or polymers) are also known, however, since the first goldphosphazene complexes were reported in 1983 by Allcock et al, [9] only a few exploratory examples have been described, and mostly for gold. Methylphenylphosphazenes were used as a stabilizing medium in the solution-phase synthesis of gold nanoparticles by Wisian-Neilson et al [10] and structurally characterized silver(I) coordination polymers were obtained by Steiner et al [11] The only structurally characterized gold-phosphazene complex has been described recently. [12] These results, together with our experience in the chemistry of gold and silver, prompted us to prepare new cyclic and polymeric phosphazenes containing gold or silver.…”

Organometallic Derivatives of Cyclotriphosphazene as Precursors of Nanostructured Metallic Materials: A New Solid State Method

“…Wisian-Neilson [21] prepared Au nanoparticles using the method of Brust-Schiffrin in water/toluene, stabilizing the nanoparticles with thioether groups anchored to a polyphosphazene backbone (all of these methods are in solution). We have recently reported the first solid-phase synthesis of metal nanoparticles using polyphosphazene as a hybrid inorganic-organic template [22][23][24][25], shown in Scheme 1.…”

Synthesis and Characterization of Organometallic Polyphosphazenes and Their Applications in Nanonoscience

“…Walker et al [29] prepared gold nanoparticles by reducing AuCl 4 À with NaBH 4 in the presence of PMPP [poly(methylphenylphosphazene)] using a biphasic water-toluene system. Recently, Jung et al [30] prepared gold nanoparticles using the method of Brust-Schiffrin in water-toluene and stabilizing the nanoparticles with thioether groups anchored to a polyphosphazene backbone. In all these methods the nanoparticles are generated in solution by an independent method, and the polyphosphazene acts as a matrix to stabilize them.…”