Synthesis, Characterization, and Interlayer Distance Study of Zirconium Phosphonates with Stoichiometric Variation of Methyl and p-Aminobenzyl Pendant Groups

Willem R. Leenstra, Jay Amicangelo

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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 languageEnglish (US)
Pages (from-to)5317-5323
Number of pages7
JournalInorganic Chemistry
Volume37
Issue number20
StatePublished - Dec 1 1998

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Organophosphonates
interlayers
Molecular mechanics
Chemical shift
synthesis
Surface waters
Stoichiometry
Phosphorus
Conformations
Thermogravimetric analysis
Nuclear magnetic resonance
hydrochlorides
linearity
chemical equilibrium
phosphorus
stoichiometry
spacing
deviation
nuclear magnetic resonance
rings

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

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title = "Synthesis, Characterization, and Interlayer Distance Study of Zirconium Phosphonates with Stoichiometric Variation of Methyl and p-Aminobenzyl Pendant Groups",
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.",
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T1 - Synthesis, Characterization, and Interlayer Distance Study of Zirconium Phosphonates with Stoichiometric Variation of Methyl and p-Aminobenzyl Pendant Groups

AU - Leenstra, Willem R.

AU - Amicangelo, Jay

PY - 1998/12/1

Y1 - 1998/12/1

N2 - 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.

AB - 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.

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