Abstract
A new class of layered zirconium mixed phosphonates, zirconium (p-aminobenzy])phosphonate methylphosphonate, Zr(O3PCH2C6H4NH2) x(O3PCH3)2-x [abbreviated as Zr(pab)x(me)2-x], and its intercalated hydrochloride form, Zr(O3PCH2C6H4NH3Cl) x(O3PCH3)2-x [Zr(pabHCl)x(me)2-x], in a number of stoichiometric pendant group ratios, have been synthesized and characterized. For these materials, thermogravimetric analysis was able to identify and quantify, when present, loss of surface-adsorbed water, HCl units, methyl and p-aminobenzyl groups. 31P NMR indicated evidence of two types of phosphorus environments that tracked the stoichiometry but behaved differently in chemical shift variation (6.7-8.5 and 2.2-8.0 ppm). FT-IR measurements quantitatively accounted for relative mole fraction as the pendant group ratio was varied. Interlayer spacing measurements as a function of the stoichiometric ratio were carried out by XRD and corroborated by molecular mechanics calculations. The calculations show that interlayer pendant group conformations (rotations about the anchoring P-C bond and of the benzenoid ring) are responsible ford-space variational behavior. It is observed that while Vegard's law is obeyed to some extent, deviation from linearity can be understood in terms of packing forces.
Original language | English (US) |
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Pages (from-to) | 5317-5323 |
Number of pages | 7 |
Journal | Inorganic chemistry |
Volume | 37 |
Issue number | 20 |
DOIs | |
State | Published - 1998 |
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Inorganic Chemistry