Small-molecule model phosphazenes with para-substituted phenoxy side groups: Synthesis, crystal structures and comparisons with corresponding high polymers

A series of new cyclic phosphazenes and a linear short-chain phosphazene have been synthesized as models for the preparation of the corresponding phosphazene high polymers. Several of the high polymers were also prepared. The small molecule compounds were characterized by a combination of P-31 NMR, mass spectrometry and elemental analysis. The crystal and molecular structures of N3P3(OC(6)H(4)R-4)(6) (R = CH3, OH, OPh or OCH(2)Ph), N4P4(OC(6)H(4)OPh-4)(8) and OP(OC(6)H(4)Bu(t)-4)(2)NP(OC(6)H(4)Bu(t)-4) were investigated by single-crystal X-ray diffraction techniques. High polymers, [NP(OC(6)H(4)R-4)(2)](n), (R = OPh, OCH(2)Ph or Bu(t)), [NP(OC(6)H(4)CPh(3)-4)(1.5)Cl-0.5](n), and [NP(OCH(2)C(6)H(4)OCH(2)Ph-4)(2)](n) were also prepared and their structures confirmed by a variety of techniques including H-1 and P-31 NMR spectroscopy, elemental analysis and differential scanning calorimetry.