Abstract: | A series of coordination polymers, poly[bis(phosphinatoalanyl)phosphonates], [X(Y)AlOP(R)(O)OAl(Y′)(X′)]n, were synthesized in which the terminal alanyl substituents (X,Y,X,′Y′) consisted of phosphinato (OPRR′O) or fluoro (F) moieties. The properties of the polymers were primarily dependent upon the type of terminal substituent and the hydrocarbon moieties (R,R′) on phosphorus. Polymers with four phosphinato moieties gave molecular weights M?n to 120000 with intrinsic viscosities [η] from 1.5 to 18; the corresponding solids were partially crystalline, melted before decomposition, and were film-forming when larger phosphorus substituents were incorporated. Sequential replacement of the phosphinato moieties with fluorine resulted in molecular weights below 10000 and low viscosities. The properties of the polymers are examined, and the roles of substituents on probable structures are discussed. |