Issue 12, 2020

Structural variability of pendant groups within the interlayer region of zirconium arene-phosph(on)ates: chemical and structural characterization of oxy- and methyl-linked 2-naphthyl phosphonates, and mixed oxy-linked derivatives

Abstract

Several new zirconium phosphonates incorporating the naphthalene ring and having the general formula Zr(O3PR)1(O3PR′)1 [R and R′ = –CH2C10H7, –OC10H7, –CH3, –OC2H5, –OH] have been synthesized. These materials were chemically characterized using thermal gravimetric analysis (percentage of organic content), infrared spectroscopy (presence of the desired organic functional groups), and solid-state 31P NMR (phosphorus environments), while the structural parameters were determined using X-ray powder diffraction (interlayer d spacings). The two new zirconium bis(phosphonates), Zr(O3PC10H7)2 and Zr(O3PCH2C10H7)2, were found to have d spacings of 19.6 and 20.0 Å, respectively. Three of the four zirconium mixed phosphonates examined are found to be single-phase structures with random mixtures of the organic moieties within the interlayer, and possess d spacings (14.3, 15.3, and 16.1 Å) that are between those of the two parent zirconium bis(phosphonates). The fourth is found to be a staged or segregated structure and possesses a d spacing that is approximately a sum of the two parent zirconium bis(phosphonates), with a d spacing of 28.2 Å. Solid-state 31P NMR of Zr(O3PCH2C10H7)2 revealed the presence of two isotropic resonances, which is interpreted in terms of two distinct, “locked-in” conformations of the –CH2C10H7 group. The experimental d spacings of the zirconium bis(phosphonates) correlate well with a simple predictive model based on the effective length and predominant conformation of the organic functional group.

Graphical abstract: Structural variability of pendant groups within the interlayer region of zirconium arene-phosph(on)ates: chemical and structural characterization of oxy- and methyl-linked 2-naphthyl phosphonates, and mixed oxy-linked derivatives

Supplementary files

Article information

Article type
Paper
Submitted
30 sep 2019
Accepted
01 dec 2019
First published
03 dec 2019

Dalton Trans., 2020,49, 3796-3808

Structural variability of pendant groups within the interlayer region of zirconium arene-phosph(on)ates: chemical and structural characterization of oxy- and methyl-linked 2-naphthyl phosphonates, and mixed oxy-linked derivatives

J. C. Amicangelo and W. R. Leenstra, Dalton Trans., 2020, 49, 3796 DOI: 10.1039/C9DT03875B

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