Benzene‐ d 6 and toluene‐ d 8 as guest molecules in micropores of a layered zirconium phosphonate: 2 H, 13 C{ 1 H}, and 31 P{ 1 H} solid‐state NMR, deuterium NMR relaxation, and molecular motions

Contreras, Aida R.; Bakhmutov, Vladimir I.; Elliott, Douglas W.; Clearfield, Abraham

doi:10.1002/mrc.4779

Title: Benzene‐ d ₆ and toluene‐ d ₈ as guest molecules in micropores of a layered zirconium phosphonate: ² H, ¹³ C{ ¹ H}, and ³¹ P{ ¹ H} solid‐state NMR, deuterium NMR relaxation, and molecular motions

Journal Article · Sun Jul 29 00:00:00 EDT 2018 · Magnetic Resonance in Chemistry

DOI:https://doi.org/10.1002/mrc.4779· OSTI ID:1462117

Contreras, Aida R. ^[1];

^[1]; Elliott, Douglas W. ^[1]; Clearfield, Abraham ^[1]

Department of Chemistry Texas A&,M University College Station Texas USA

Abstract For the first time, pore spaces in the Zr (IV) phosphonate ( 1 ) as a representative of layered metal (IV) phosphonate materials have been investigated by studying mobility of guest molecules, benzene‐ d ₆ , and toluene‐ d ₈ . Guest molecules located in micropores of 1 have been characterized by solid‐state ¹³ C{ ¹ H} and ² H NMR spectra in static samples with varying temperatures. At moderately low temperatures, the benzene and toluene molecules experience fast isotropic reorientations and show the motionally averaged liquid‐like carbon and deuterium line shapes in the NMR spectra. At lower temperatures, two anisotropic motional modes have been found for benzene molecules by analyzing the ² H NMR line shapes: the well‐known in‐plane C ₆ rotation and composite motions. Interpretation of the variable‐temperature ² H T ₁ relaxation times identifies the composite motions as 120° flips around the C ₆ axis perpendicular to the molecular plane and the rotations around the molecular para ‐C‐C axis. The data obtained resulted in the idealized (cylinder‐shaped) model of micropores in compound 1 with the diameter of 20–30 Å. Furthermore, the activation energy of 20.1 kJ/mol determined for the benzene motions classifies the molecule–surface interactions as weak but enough for absorption.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: DE‐NE0000746

OSTI ID:: 1462117

Journal Information:: Magnetic Resonance in Chemistry, Journal Name: Magnetic Resonance in Chemistry Vol. 56 Journal Issue: 12; ISSN 0749-1581

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

Citation Metrics:

Cited by: 3 works

Citation information provided by
Web of Science

References (24)

Nanoencapsulation of Insulin into Zirconium Phosphate for Oral Delivery Applications Díaz, Agustín; David, Amanda; Pérez, Riviam Biomacromolecules, Vol. 11, Issue 9 https://doi.org/10.1021/bm100659p	journal	September 2010
Layered metal(IV) phosphonate materials: Solid-state ¹ H, ¹³ C, ³¹ P NMR spectra and NMR relaxation Sheikh, Javeed Ahmad; Bakhmutov, Vladimir I.; Clearfield, Abraham Magnetic Resonance in Chemistry, Vol. 56, Issue 4 https://doi.org/10.1002/mrc.4698	journal	January 2018
Organically pillared microporous zirconium phosphonates Clearfield, Abraham; Wang, Zhike Journal of the Chemical Society, Dalton Transactions, Issue 15 https://doi.org/10.1039/b202371g	journal	July 2002
Synthesis and NMR T1 relaxation study of rhenium and manganese hydride complexes Gusev, Dmitry G.; Nietlispach, Daniel; Vymenits, Alexey B. Inorganic Chemistry, Vol. 32, Issue 15 https://doi.org/10.1021/ic00067a013	journal	July 1993
Guest Molecular Motion of [N(CH ₃ ) ₄ ][Cd ₃ (CN) ₇ ] Benzene, Toluene, and Ethylbenzene Clathrates As Studied by ² H NMR Nishikiori, Shin-ichi; Kitazawa, Takafumi; Kim, Chong-Hyeak The Journal of Physical Chemistry A, Vol. 104, Issue 12 https://doi.org/10.1021/jp9926286	journal	March 2000
Layered α-Zirconium Phosphates and Phosphonates Kumar, Challa V.; Bhambhani, Akhilesh; Hnatiuk, Nathan ChemInform, Vol. 35, Issue 36 https://doi.org/10.1002/chin.200436233	journal	September 2004
Zirconium phosphate nano-platelets: a novel platform for drug delivery in cancer therapy Díaz, Agustín; Saxena, Vipin; González, Julissa Chemical Communications, Vol. 48, Issue 12 https://doi.org/10.1039/c2cc16218k	journal	January 2012
Dynamics and disposition of benzene guest molecules in the micropore channels of a flexible metal-organic framework studied by 2H NMR and X-ray crystallography Ratcliffe, C. I.; Soldatov, D. V.; Ripmeester, J. A. Microporous and Mesoporous Materials, Vol. 73, Issue 1-2 https://doi.org/10.1016/j.micromeso.2003.11.020	journal	August 2004
NMR studies of the sorption of p-xylene, toluene, and benzene on ZSM 5 zeolite Kustanovich, I.; Vieth, H. M.; Luz, Z. The Journal of Physical Chemistry, Vol. 93, Issue 21 https://doi.org/10.1021/j100358a034	journal	October 1989
Deuterium NMR studies of framework and guest mobility in the metal–organic framework compound MOF-5, Zn4O(O2CC6H4CO2)3 Gonzalez, Jorge; Nandini Devi, R.; Tunstall, David P. Microporous and Mesoporous Materials, Vol. 84, Issue 1-3 https://doi.org/10.1016/j.micromeso.2005.04.019	journal	September 2005
Deuterium NMR Studies of Local Motions of Benzene Adsorbed on Ca-Montmorillonite Xiong, Jincheng; Maciel, Gary E. The Journal of Physical Chemistry B, Vol. 103, Issue 26 https://doi.org/10.1021/jp990813d	journal	July 1999
Phenylalanine ring dynamics by solid-state deuterium NMR Gall, C. M.; DiVerdi, J. A.; Opella, S. J. Journal of the American Chemical Society, Vol. 103, Issue 17 https://doi.org/10.1021/ja00407a012	journal	August 1981
Zirconium(IV) Phosphonate–Phosphates as Efficient Ion-Exchange Materials Silbernagel, Rita; Martin, Caroline H.; Clearfield, Abraham Inorganic Chemistry, Vol. 55, Issue 4 https://doi.org/10.1021/acs.inorgchem.5b02555	journal	January 2016
NADH Electrooxidation Using Bis(1,10-phenanthroline-5,6-dione)(2,2′-bipyridine)ruthenium(II)-Exchanged Zirconium Phosphate Modified Carbon Paste Electrodes Santiago, Mitk'El B.; Vélez, Meredith M.; Borrero, Solmarie Electroanalysis, Vol. 18, Issue 6 https://doi.org/10.1002/elan.200503432	journal	March 2006
Orientations of the principal components of electric field gradients and internal motions in dihydrogen ligands from the2HT1 NMR relaxation data in solution Bakhmutov, Vladimir I. Magnetic Resonance in Chemistry, Vol. 42, Issue 1 https://doi.org/10.1002/mrc.1313	journal	December 2003
Structural and dynamical properties of guest molecules confined in mesoporous silica materials revealed by NMR Buntkowsky, Gerd; Breitzke, Hergen; Adamczyk, Anna Physical Chemistry Chemical Physics, Vol. 9, Issue 35 https://doi.org/10.1039/b707322d	journal	January 2007
Intercalation of tris-(2,2′-bipyridyl) ruthenium (II) in α- and γ-zirconium phosphate: synthesis, thermal behaviour and X-ray characterization Ferragina, Carla; Di Rocco, Romolo; Giannoccaro, Potenzo Journal of Inclusion Phenomena and Macrocyclic Chemistry, Vol. 63, Issue 1-2 https://doi.org/10.1007/s10847-008-9500-y	journal	September 2008
Capturing Guest Dynamics in Metal–Organic Framework CPO-27-M (M = Mg, Zn) by ² H Solid-State NMR Spectroscopy Xu, Jun; Sinelnikov, Regina; Huang, Yining Langmuir, Vol. 32, Issue 22 https://doi.org/10.1021/acs.langmuir.6b00851	journal	May 2016
The structure and dynamics of benzene in zeolite L Newsam, J. M.; Silbernagel, B. G.; Garcia, A. R. Journal of the Chemical Society, Chemical Communications, Issue 9 https://doi.org/10.1039/c39870000664	journal	January 1987
Diffusion of Benzene in the Breathing Metal–Organic Framework MIL-53(Cr): A Joint Experimental–Computational Investigation Kolokolov, D. I.; Jobic, H.; Rives, S. The Journal of Physical Chemistry C, Vol. 119, Issue 15 https://doi.org/10.1021/acs.jpcc.5b01465	journal	April 2015
Pillared metal(IV) phosphate-phosphonate extraction of actinides Burns, J. D.; Clearfield, A.; Borkowski, Marian Radiochimica Acta, Vol. 100, Issue 6 https://doi.org/10.1524/ract.2012.1929	journal	June 2012
Motion of Aromatic Hydrocarbons in the Microporous Aluminum Methylphosphonates AlMePO-α and AlMePO-β Gonzalez, Jorge; Devi, R. Nandini; Wright, Paul A. The Journal of Physical Chemistry B, Vol. 109, Issue 46 https://doi.org/10.1021/jp052590z	journal	November 2005
² H-Solid-State NMR Study of Benzene- d ₆ Confined in Mesoporous Silica SBA-15 Gedat, E.; Schreiber, A.; Albrecht, J. The Journal of Physical Chemistry B, Vol. 106, Issue 8 https://doi.org/10.1021/jp012391p	journal	February 2002
NMR studies of wood and wood products Maunu, S. L. Progress in Nuclear Magnetic Resonance Spectroscopy, Vol. 40, Issue 2 https://doi.org/10.1016/S0079-6565(01)00041-3	journal	February 2002

Similar Records

Pyridine-d₅ as a ²H NMR probe for investigation of macrostructure and pore shapes in a layered Sn(iv) phosphonate–phosphate material

Journal Article · Fri Feb 21 00:00:00 EST 2020 · ChemComm · OSTI ID:1462117

Bakhmutov, Vladimir I.; Elliott, Douglas W.; Wylie, Gregory P.; +3 more

/sup 1/H and /sup 13/C NMR studies on carbon dioxide hydrate

Journal Article · Thu Mar 27 00:00:00 EST 1986 · J. Phys. Chem.; (United States) · OSTI ID:1462117

Ratcliffe, C I; Ripmeester, J A

Guest-host interactions in sodium zeolite Y: Structural and dynamical [sup 23]Na double-rotation NMR study of H[sub 2]O, PMe[sub 3], Mo(CO)[sub 6], and Mo(CO)[sub 4](PMe[sub 3])[sub 2] adsorption in Na[sub 56]Y

Journal Article · Wed Jan 27 00:00:00 EST 1993 · Journal of the American Chemical Society; (United States) · OSTI ID:1462117

Jelinek, R; Oezkar, S; Malek, A; +2 more

Title: Benzene‐ d 6 and toluene‐ d 8 as guest molecules in micropores of a layered zirconium phosphonate: 2 H, 13 C{ 1 H}, and 31 P{ 1 H} solid‐state NMR, deuterium NMR relaxation, and molecular motions

Citation Formats

References (24)

Similar Records

Related Subjects

Title: Benzene‐ d ₆ and toluene‐ d ₈ as guest molecules in micropores of a layered zirconium phosphonate: ² H, ¹³ C{ ¹ H}, and ³¹ P{ ¹ H} solid‐state NMR, deuterium NMR relaxation, and molecular motions