To further elucidate the effects of atomic and bonding variations within metal coordination polymers on the properties of the bulk polymer, two new metal coordination polymers containing zirconium(IV) have been synthesized and characterized. Through the condensation polymerization of tetrakis(salicylaldhydato)zirconium(IV), Zr(sal)$\sb4$, and 3,3$\sp\prime,4,4\sp\prime$-tetra-aminodiphenylmethane or the chelation polymerization of Zr(sal)$\sb4$ and N,N$\sp\prime,\rm N\sp{\prime\prime},N\sp{\prime\prime\prime}$-tetrasalicylidene-$3,3\sp \prime,4,4\sp\prime$-tetraaminodiphenylmethane, H$\sb4$tstm, the polymer catena-poly (zirconium(IV)($\mu-\rm N,N\sp\prime,N\sp{\prime\prime},N\sp{\prime\prime\prime}$-tetrasalicylidene 3,3$\sp\prime,4,4\sp\prime$-tetraaminobiphenylmethanato-O,N,N$\sp\prime,\rm O\sp{\prime}$:$\rm O\sp{\prime\prime},N\sp{\prime\prime},N\sp{\prime\prime\prime},O\sp{\prime\prime\prime}$)), (Zr(tstm)) $\sb{\rm n}$, was prepared. Similarly, reaction of Zr(sal)$\sb4$ with 3,3$\sp\prime,4,4\sp\prime$-tetraaminodiphenylsulfone yielded catena-poly (zirconium(IV)($\mu$-$\rm N,N\sp\prime,N\sp{\prime\prime},N\sp{\prime\prime\prime}$-tetrasalicylidene-$3,3\sp\prime,4,4\sp\prime$-tetraamino-biphenylsulfonato-$\rm O,N,N\sp\prime,O \sp\prime$:$\rm O\sp{\prime\prime},N\sp{\prime\prime},N\sp{\prime\prime\prime}, O\sp{\prime\prime\prime})\rbrack$, (Zr(tsts)) $\sb{\rm n}$. Due to the instability of N,N$\sp\prime,\rm N\sp{\prime\prime},N\sp{\prime\prime\prime}$-tetrasalicylidene-$3 ,3\sp\prime,4,4\sp\prime$-tetraaminodiphenylsulfone,$\ H\sb4$tsts, in the polymerization solvent dimethylsulfoxide, the reaction of Zr(sal)$\sb4$ and H$\sb4$tsts yielded only oligomeric material. Molecular weight determinations by GPC on fractionated polymer samples in N-methylpyrrolidinone gave polystyrene equivalent molecular weights in excess of 13,000 for (Zr(tstm)) $\sb{\rm n}$ by both synthetic procedures described above and 8,700 for (Zr(tsts)) $\sb{\rm n}$ prepared via condensation polymerization. After capping the metal ends of the polymers with a N,N$\sp\prime$-bis(5-tert-butylsalicylidene)-1,2-diaminobenzenato(2-) group, end group analysis by $\sp1$H-NMR corroborated these data. The polymers were also characterized by IR and UV-vis spectroscopies. Thermal analyses of the polymers showed that they are air stable to greater than 400$\sp\circ$C. These new polymers were compared to another zirconium polymer, catena-poly (zirconium(IV)($\mu$-$\rm N,N\sp\prime ,N\sp{\prime\prime},N\sp{\prime\prime\prime}$-tetrasalicylidene-$3,3\sp\prime$-diaminobenzinato-$\rm O,N,N\sp\prime,O\sp\prime{:}O\sp{\prime\prime},N\sp{\prime \prime},N\sp{\prime\prime\prime},O\sp{\prime\prime\prime})\rbrack$, (Zr(tsdb)) $\sb{\rm n}$, and their cerium(IV) analogs, (Ce(tsdb)) $\sb{\rm n}$, (Ce(tstm)) $\sb{\rm n}$, and (Ce(tsts)) $\sb{\rm n}$. Films of the polymers cast on chrome-plated steel were found to be continuous by scanning electron microscopy. Electrical experiments on films of the six polymers cast on glass gave conductivities of 10$\sp{-7}$ S/cm. These conductivities were increased by a factor of 10$\sp{4}$ by doping with iodine.
| Identifer | oai:union.ndltd.org:UMASS/oai:scholarworks.umass.edu:dissertations-9088 |
| Date | 01 January 1995 |
| Creators | Cronin, Jon Andrew |
| Publisher | ScholarWorks@UMass Amherst |
| Source Sets | University of Massachusetts, Amherst |
| Language | English |
| Detected Language | English |
| Type | text |
| Source | Doctoral Dissertations Available from Proquest |
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