Synthesis of poly (metallophosphazenes) and novel poly (organophosphazenes)

New materials are needed that can meet the ever-increasing demands of modern technology. Inorganic macromolecules provide a means of preparing materials that have properties that are intermediate between those of conventional organic polymers and inorganic materials. This thesis is concerned with the synthesis of two different classes of inorganic macromolecules: polymetallophosphazenes, inorganic polymers that contain transition metals as part of their structure; and poly-(organophosphazenes), hybrid organic-inorganic polymers that may have useful optical properties.; A synthetic procedure has been developed for the preparation of 1-phenyl-1-(carbonylcyclopentadienylmetallo)-3,3,5,5-tetrachlorocyclo-triphosphazenes. These are prepared by the interaction of lithium (1-phenyl-3,3,5,5-tetrachlorocyclotriphosphazen-1-yl)triethylborate and M({dollar}etasp5{dollar}-C{dollar}sb5{dollar}H{dollar}sb5{dollar})(CO){dollar}sb{lcub}rm n{rcub}{dollar}I (M = Cr, Mo, W, n = 3; M = Fe, Ru, n = 2) in tetrahydrofuran.; The first high polymeric phosphazenes with skeletal phosphorous-transition-metal covalent bonds are described. These species have been synthesized by two routes: (a) by the interaction of the organometallic nucleophile, (FeCp(CO){dollar}sb2)sp-{dollar}, with mixed-substituent polyphosphazenes bearing both chloro- and trifluoroethoxy groups; and (b) by the reaction of FeCp(CO){dollar}sb2{dollar}I with a polyphosphazene that bears both trifluoro-ethoxy substituents and anionic sites at the skeletal phosphorus atoms. Small molecule compounds were used as models for the structural characteristics of the polymers.; The effects of steric hindrance on the synthesis of poly(aryloxyphosphazenes) bearing bulky aryloxy or phenylphenoxy substituents are discussed. The syntheses of poly(aryloxyphosphazenes) with the general formula (NP(OAr{dollar}sp1{dollar}){dollar}sb{lcub}rm x{rcub}{dollar}(OAr{dollar}sp2{dollar}){dollar}sb{lcub}rm y{rcub}{dollar}) {dollar}sb{lcub}rm n{rcub}{dollar}, where OAr{dollar}sp1{dollar} and OAr{dollar}sp2{dollar} are phenoxy, 2-methylphenoxy, 4-methylphenoxy, 2-phenylphenoxy, 3-phenylphenoxy, 4-phenylphenoxy, 4-benzylphenoxy, 4-cumylphenoxy, and 4-tert-butylphenoxy, and x + y = 2, are described. These polymers were prepared by the interaction of the corresponding sodium aryloxide with poly(dichlorophosphazene) in dioxane at 150{dollar}spcirc{dollar}C in an autoclave. The influence of side group structural parameters on the thermal transition behavior of the polymers is discussed. The refractive indices of the polymers were found to vary between 1.562 and 1.686.; Molecular motion in solid poly(aryloxyphosphazenes) was investigated using deuterium NMR spectroscopy. Specifically labelled poly(di-phenoxyphosphazene) and a mixed-substituent phenoxy-phenyl-polyphosphazene were examined. Lineshape analyses showed that at least four types of side group motion exist in solid poly(aryloxyphosphazenes). Large changes in side group motion were apparent in the spectra at temperatures above and below the glass transition temperatures, although no significant changes in side group motion were detected precisely at the glass transition temperature.