Eight-coordinate Schiff-base zirconium polymers: Synthesis, characterization and properties

The condensation polymerization of tetrakis (salicylaldhydato) zirconium(IV) (Zr(sal)(4)) and 3,3',4,4'-tetraaminodiphenylmethane, produces the polymer catena-poly [zirconium(IV) (mu-N,N',N '',N'''-tetrasalicylidene-3,3',4,4'-tetraaminobiphenylmethanato-O,N',N',O':-O '',N '',N'''O''')] ([Zr(tstm>](n)), with a number-average molecular mass <(M)over bar (n)>, above 13000 based on gel permeation chromatography and nuclear magnetic resonance end-group evaluations. Reaction of Zr(sal)(4) with 3,3',4,4'-tetraaminodiphenylsulfone yields catena-poly-[zirconium(IV) (mu-N,N',N '', N'''-tetrasalicylidene-3,3',4,4'-tetraaminobiphenylsulfonato-O,N,N',O':O '', N '',N''',O''')] ([Zr(tsts)](n)) with M(n) above 8700. The polymers show thermal stability above 400 degrees C in air. Films of these polymers and catena-poly [zirconium(IV) (mu-N,N',N '',N'''-tetrasalicylidene-3,3'-diaminobenzinato-O.N,N',O:O '',N '',N '',O''')] ([Zr(tsdb)](n)) and the cerium(IV) analogs, [Ce(tsdb)](n), [Ce(tstm)](n) and [Ce(tsts)](n) cast on chrome-plated steel were found to be continuous by scanning electron microscopy, and they have conductivities on glass of similar to 10(-7) S cm(-1) (increased by a factor of similar to 10(4) by I-2 doping).