skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Tetraalkylphosphonium polyoxometalate ionic liquids : novel, organic-inorganic hybrid materials.

Abstract

Pairing of a Keggin or Lindqvist polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation is shown to yield the first members of a new family of ionic liquids (ILs). Detailed characterization of one of them, an ambient-temperature 'liquid POM' comprising the Lindqvist salt of the trihexyl(tetradecyl) phosphonium cation, by voltammetry, viscometry, conductimetry, and thermal analysis indicates that it exhibits conductivity and viscosity comparable to those of the one previously described inorganic-organic POM-IL hybrid but with substantially improved thermal stability.

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1001153
Report Number(s):
ANL/CHM/JA-57996
Journal ID: ISSN 1520--6106; ISSN 1520--5207; TRN: US201101%%877
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Phys. Chem. B; Journal Volume: 111; Journal Issue: 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMBIENT TEMPERATURE; ANIONS; CATIONS; STABILITY; THERMAL ANALYSIS; VISCOSITY

Citation Formats

Rickert, P. G., Antonio, M. P., Firestone, M. A., Kubatko, K.-A., Szreder, T., Wishart, J. F., Dietz, M. L., Chemistry, Univ. of Notre Dame, and BNL. Tetraalkylphosphonium polyoxometalate ionic liquids : novel, organic-inorganic hybrid materials.. United States: N. p., 2007. Web. doi:10.1021/jp0671751.
Rickert, P. G., Antonio, M. P., Firestone, M. A., Kubatko, K.-A., Szreder, T., Wishart, J. F., Dietz, M. L., Chemistry, Univ. of Notre Dame, & BNL. Tetraalkylphosphonium polyoxometalate ionic liquids : novel, organic-inorganic hybrid materials.. United States. doi:10.1021/jp0671751.
Rickert, P. G., Antonio, M. P., Firestone, M. A., Kubatko, K.-A., Szreder, T., Wishart, J. F., Dietz, M. L., Chemistry, Univ. of Notre Dame, and BNL. Mon . "Tetraalkylphosphonium polyoxometalate ionic liquids : novel, organic-inorganic hybrid materials.". United States. doi:10.1021/jp0671751.
@article{osti_1001153,
title = {Tetraalkylphosphonium polyoxometalate ionic liquids : novel, organic-inorganic hybrid materials.},
author = {Rickert, P. G. and Antonio, M. P. and Firestone, M. A. and Kubatko, K.-A. and Szreder, T. and Wishart, J. F. and Dietz, M. L. and Chemistry and Univ. of Notre Dame and BNL},
abstractNote = {Pairing of a Keggin or Lindqvist polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation is shown to yield the first members of a new family of ionic liquids (ILs). Detailed characterization of one of them, an ambient-temperature 'liquid POM' comprising the Lindqvist salt of the trihexyl(tetradecyl) phosphonium cation, by voltammetry, viscometry, conductimetry, and thermal analysis indicates that it exhibits conductivity and viscosity comparable to those of the one previously described inorganic-organic POM-IL hybrid but with substantially improved thermal stability.},
doi = {10.1021/jp0671751},
journal = {J. Phys. Chem. B},
number = 2007,
volume = 111,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • Two novel inorganic-organic hybrid materials based on an organic dye cation methylene blue (MB) and Lindqvist-type POM polyanions, [C{sub 22}H{sub 18}N{sub 3}S]{sub 2}Mo{sub 6}O{sub 19} 2DMF (1) and [C{sub 22}H{sub 18}N{sub 3}S]{sub 2}W{sub 6}O{sub 19} 2DMF (2) were synthesized under ambient conditions and characterized by CV, IR spectroscopy, solid diffuse reflectance spectrum, UV-vis spectra in DMF solution, luminescent spectrum and single crystal X-ray diffraction. Crystallographic data reveal that compounds 1 and 2 are isostructural and both crystallize in the triclinic space group P1-bar . Their crystal structures present that the layers of organic molecules and inorganic anions array alternatively, andmore » there exist strong {pi}...{pi} stacking interactions between dimeric MB cations and near distance interactions among organic dye cations, Lindqvist-type POM polyanions and DMF molecules. The solid diffuse reflectance spectra and UV-vis spectra in DMF solution appear new absorption bands ascribed to the charge-transfer transition between the cationic MB donor and the POM acceptors. Studies of the photoluminescent properties show that the formation of 1 and 2 lead to the fluorescence quenching of starting materials. -- Graphical abstract: Their crystal structures present that the layers of organic molecules and inorganic anions array alternatively, and there exist strong {pi}...{pi} stacking interactions between dimeric MB cations. Display Omitted« less
  • The solid hybrid material (H{sub 3/4}pbpy){sub 4}[PMo{sub 12}O{sub 40}].1.25H{sub 2}O (1) (pbpy=5-phenyl-2-(4-pyridinyl)pyridine) has been prepared and characterized. A structural feature of compound 1 is that the polyoxometalate anions exhibit a one-dimensional inorganic double chain-like structure via weak interactions of O...O. The organic moiety exhibits regular packing with offset aromatic-aromatic interactions between the pbpys, leading to a compact supramolecular framework structure to accommodate the inorganic chains. Compound 1 was employed to fabricate the three-dimensional bulk-modified carbon paste electrode (1-CPE) to research on its electrochemistry properties. The results indicate that 1 retained Keggin molybdate anion electrocatalytic activities toward the reduction of chlorate,more » hydrogen peroxide and nitrite.« less
  • A one-dimensional coordination polymer [Cu(en){sub 2}]{sub 2}[Cu(en){sub 2}(H{sub 2}O)]{sub 2}{l_brace}[Cu(en){sub 2}]{sub 2}[Cu{sub 2}Si{sub 2}W{sub 22}O{sub 78}]{r_brace}.4.5H{sub 2}O (en=ethylenediamine), which represents the first example of one-dimensional organic-inorganic hybrid based on the bimolecular Keggin polyoxometalates {l_brace}[Cu(en){sub 2}]{sub 2}[Cu{sub 2}Si{sub 2}W{sub 22}O{sub 78}]{r_brace}{sup 8-} has been hydrothermally synthesized and characterized by elemental analyses, IR, TG and single crystal X-ray diffraction. Crystal data: C{sub 24}H{sub 85}Cu{sub 8}N{sub 24}O{sub 84.5}Si{sub 2}W{sub 22}, monoclinic, P2{sub 1}/c, a=18.8126(3), b=23.0896(4), c=26.0711(4) A, {beta}=96.3790(10){sup o}, V=11254.5(3) A{sup 3}, T=293(2) K; Z=4, {mu}=23.983 mm{sup -1}, R {sub 1}=0.0628, wR {sub 2}=0.1210 [I>2{sigma}], R {sub 1}=0.0854, wR {sub 2}=0.1285 (all datamore » ). - Graphical abstract: A one-dimensional coordination polymer which represents the first example of 1D organic-inorganic hybrid based on the bimolecular Keggin POMs {l_brace}[Cu(en){sub 2}]{sub 2}[Cu{sub 2}Si{sub 2}W{sub 22}O{sub 78}]{r_brace}{sup 8-} has been hydrothermally synthesized and characterized.« less
  • Three new organic–inorganic hybrid compounds, namely [Cu{sup I}L{sub p}]{sub 2}[W{sub 6}O{sub 19}]·H{sub 2}O (1), [Cu{sup I}L{sub p}]{sub 3}[W{sub 6}O{sub 19}]Cl (2) and [Cu{sup I}L{sub p}]{sub 2}[W{sub 6}O{sub 19}]·2H{sub 2}O (3) (L{sub p}=α,α′-bis-[3-(2-pyridyl)pyrazol-1-yl]-1,4-dimethylbenzene) based on copper(I) ion, a neutral N-donor bichelate-bridging ligand (L{sub p}) and a Lindqvist-type polyoxometalate (POM) [W{sub 6}O{sub 19}]{sup 2−}, have been hydrothermally prepared under different synthetic conditions and structurally characterized by elemental analyses, IR spectra, TG analyses, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction analyses. Compounds 1 and 2 contain two different but topologically similar meso-helical chainlike coordination moieties. Compound 3 contains both left- and right-handedmore » chiral “mobius strip” units. These cationic meso-helical chains and “mobius strip” units in compounds 1–3 are further combined with Lindqvist-type polyoxoanions to form 3-D supramolecular assemblies through extensive electrostatic forces and/or π–π interactions. The photo-luminescent properties of 1–3 have also been investigated, which are mainly attributed to the L{sub p} ligand-centered emission. - Graphical abstract: Three new hybrid compounds based on same Cu(I) ion, bichelate-bridging ligand and [W{sub 6}O{sub 19}]{sup 2−} building blocks were synthesized. Various structural features of three compounds were tuned by different synthetic conditions. - Highlights: • New compounds based on Cu(I), bichelate-bridging ligand and POM were prepared. • Compounds 1 and 2 contain two different but topologically similar meso-helical chains. • Compound 3 contains both left- and right-handed chiral “mobius strip” units. • Compounds 1–3 exhibit the ligand-centered luminescent property.« less
  • Organic–inorganic nanocomposite materials have been synthesized via sol–gel. They consist of an inorganic SiO{sub 2} matrix, in which different percentages of poly(ε-caprolactone) (PCL) have been incorporated. The formation of H-bonds among the carbonyl groups of the polymer chains and Si–OH group of the inorganic matrix has been proved by means of Fourier transform infrared spectroscopy (FT-IR) analysis and has been confirmed by solid-state nuclear magnetic resonance (NMR). X-Ray diffraction (XRD) analysis highlighted the amorphous nature of the synthesized materials. Scanning electron microscope (SEM) micrograph and atomic force microscope (AFM) topography showed their homogeneous morphology and nanostructure nature. Considering the opportunitymore » to synthesize these hybrid materials under microgravity conditions by means of magnetic levitation, superconducting quantum interference device (SQUID) magnetometry has been used to quantify their magnetic susceptibility. This measure has shown that the SiO{sub 2}/PCL hybrid materials are diamagnetic and that their diamagnetic susceptibility is independent of temperature and increases with the PCL amount. - Graphical abstract: Characterization and magnetic properties of SiO{sub 2}/PCL organic–inorganic hybrid materials synthesized via sol–gel. FT-IR, Fourier transform infrared spectroscopy; solid-state NMR: solid-state nuclear magnetic resonance; SQUID: superconducting quantum interference device. - Highlights: • Sol–gel synthesis of SiO{sub 2}/PCL amorphous class I organic–inorganic hybrid materials. • FT-IR and NMR analyses show the hydrogen bonds formation between SiO{sub 2} and PCL. • AFM and SEM analyses confirm that the SiO{sub 2}/PCL are homogenous hybrid materials. • The SQUID measures show that the simples are diamagnetic. • Diamagnetic susceptibility of SiO{sub 2}/PCL materials increases with the PCL amount.« less