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Title: Layered metal(IV) phosphonate materials: Solid-state 1 H, 13 C, 31 P NMR spectra and NMR relaxation

Authors:
 [1]; ORCiD logo [2];  [1]
  1. Department of Chemistry, Texas A&M University, College Station TX 77845-3012 USA
  2. Laboratory for Nuclear Magnetic Resonance, Department of Chemistry, Texas A&M University, College Station TX 77842-3012 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1416402
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Magnetic Resonance in Chemistry
Additional Journal Information:
Related Information: CHORUS Timestamp: 2018-01-10 04:33:21; Journal ID: ISSN 0749-1581
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Sheikh, Javeed Ahmad, Bakhmutov, Vladimir I., and Clearfield, Abraham. Layered metal(IV) phosphonate materials: Solid-state 1 H, 13 C, 31 P NMR spectra and NMR relaxation. United Kingdom: N. p., 2018. Web. doi:10.1002/mrc.4698.
Sheikh, Javeed Ahmad, Bakhmutov, Vladimir I., & Clearfield, Abraham. Layered metal(IV) phosphonate materials: Solid-state 1 H, 13 C, 31 P NMR spectra and NMR relaxation. United Kingdom. doi:10.1002/mrc.4698.
Sheikh, Javeed Ahmad, Bakhmutov, Vladimir I., and Clearfield, Abraham. 2018. "Layered metal(IV) phosphonate materials: Solid-state 1 H, 13 C, 31 P NMR spectra and NMR relaxation". United Kingdom. doi:10.1002/mrc.4698.
@article{osti_1416402,
title = {Layered metal(IV) phosphonate materials: Solid-state 1 H, 13 C, 31 P NMR spectra and NMR relaxation},
author = {Sheikh, Javeed Ahmad and Bakhmutov, Vladimir I. and Clearfield, Abraham},
abstractNote = {},
doi = {10.1002/mrc.4698},
journal = {Magnetic Resonance in Chemistry},
number = ,
volume = ,
place = {United Kingdom},
year = 2018,
month = 1
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on January 8, 2019
Publisher's Accepted Manuscript

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  • Quantum-size ZnSe, PbS, CdS, and CdSe particles 30-50 {angstrom} in diameter were grown in the interlamellar region of the layered host material Zr(O{sub 3}PCH{sub 2}CH{sub 2}CO{sub 2}H){sub 2} by reaction of H{sub 2}S or H{sub 2}Se with M{sup II}(Zr-(O{sub 3}PCH{sub 2}CH{sub 2}CO{sub 2}){sub 2}). Diffraction from the PbS particles indicated the rocksalt structure, whereas CdSe adopts the zincblende structure and grows with the (111) zone axis parallel to the host layering direction. CdSe crystallites within a single host platelet are oriented relative to each other, even though the crystallinity of the host is destroyed during particle growth. Little or nomore » reaction was found under similar conditions with M{sup II}(Zr(PO{sub 4}){sub 2}).« less
  • Solid state 67ZNn NMR spectra of model compounds for metalloproteins, such as [H2B(3, 5-Me2pz)2]2Zn (pz denotes pyrazolyl ring), have been obtained using low temperatures (10 K) to enhance the Boltzmann factor in combination with cross polarization (CP) from 1H to 67Zn. Attempts to observe spectra of other model compounds, such as [H2B(pz)2]2 Zn, were hindered by long relaxation times, of the protons. In order to decrease the proton relaxation times, the high spin six coordinate complex [HB(3, 4, 5-Me3pz)3]2Fe has been investigated as a dopant. NMR and EPR measurements have shown that this Fe(II) dopant effectively reduces the 1H spinmore » lattice relaxation time, T1, of the zinc samples in the temperature range 5 to 10 K with minimal perturbations of the 1H spin lattice relaxation time in the rotating frame, T1p. Using this methodology, we have determined the 67Zn NMR parameters of 4- and 6-coordinate zinc (II) poly (pyrazolyl)borate complexes that are useful models for systems of biological importance. These investigations have demonstrated that a temperature dependent phase transition occurs in the neighborhood of 185 K for [HB(3, 5,-Me2pz)3]2Zn. Further, the other poly (pyrazolyl)borate complexes we investigated did not show this temperature dependent behavior. This conclusion is confirmed by a combination of room temperature high field (18.8T) solid state 67Zn NMR spectroscopy and low temperature X-ray methods. The utilization of paramagnetic dopants should enable low temperature cross polarization experiments to be performed on a wide variety of nuclides that are important in bioinorganic chemistry, e.g., 25Mg. 43Ca, and 67Zn.« less
  • A new coordination polymer formulated as [C{sub 8}H{sub 10}CdO{sub 7}]{sub n}.4H{sub 2}O has been prepared via a hydrothermal procedure by using 1,4-benzenedicarboxylic (p-BDC) and Cd{sup II} salt as starting materials. The structure was determined by single-crystal X-ray diffraction and the result shows that the complex crystallizes in orthorhombic system, space group Pcca, with M{sub r}=402.62, a=7.293(2) A, b=9.980(3) A, c=19.889(6) A, V=1447.6(8) A{sup 3}, Z=4, D{sub c}=1.847 g/cm{sup 3}, F(000)=808, {mu}(MoK{alpha})=1.559 mm{sup -1}, R=0.0478, wR=0.1150, GOF=1.199. It displays a neutral layered framework along ab plane constructed by hydrogen-bonding interaction through infinite zigzag chains. Its thermal decomposition and solid-state transformation coursemore » between 30 and 550 deg. C was recorded by TG curve and XRD pattern, respectively. Interestingly, it is found that at higher temperature the crystal material was converted to uniform CdO nanowires, suggesting an effective and reasonable complex-precursor procedure for preparing one-dimensional crystalline nanomaterials. - Graphical abstract: 1D CdO nanowires have been prepared by an effective and reasonable complex-precursor procedure, in which a layered metal-organic framework assembled by 1D infinite zigzag chains was heated in the presence of oxygen at higher temperature.« less
  • Phosphonate binding sites in guanidine and ammonium surface-functionalized silica xerogels were prepared via the molecular imprinting technique and characterized using solid state {sup 31}P MAS NMR. One-point, two-point, and non-specific host-guest interactions between phenylphosphonic acid (PPA) and the functionalized gels were distinguished by characteristic chemical shifts of the observed absorption peaks. Using solid state as well as solution phase NMR analyses, absorptions observed at 15.5 ppm and 6.5 ppm were identified as resulting from the 1:1 (one-point) and 2:1 (two-point) guanidine to phosphonate interactions, respectively. Similar absorptions were observed with the ammonium functionalized gels. By examining the host-guest interactions withinmore » the gels, the efficiency of the molecular imprinting procedure with regard to the functional monomer-to-template interaction could be readily assessed. Template removal followed by substrate adsorption studies conducted on the guanidine functionalized gels provided a method to evaluate the binding characteristics of the receptor sites to a phosphonate substrate. During these experiments, {sup 29}Si and {sup 31}P MAS NMR acted as diagnostic monitors to identify structural changes occurring in the gel matrix and at the receptor site from solvent mediated processes.« less
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