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Matthew P Espe

Publications and source records attributed to Matthew P Espe.

4 recordsLinked to original sources

Sequestering perrhenate with a borate-based coordination polymer: a model for pertechnetate separation.

Crystals of the layered metal organic framework solid Pb[B(Im)4](NO3)(nH2O) can undergo exchange of the nitrate for perrhenate, a model for pertechnetate, forming Pb[B(Im)4](ReO4). We can monitor this reaction by 207Pb solid-state NMR and can isolate single crystals of the resultant material through growth in the presence of an excess of perrhenate. Such a synthetic metal-organic framework solid represents a new candidate for pertechnetate-sequestering materials.

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Observation of a deuteron nuclear magnetic resonance Knight shift in conductive polyaniline.

Solid state deuteron magic angle spinning nuclear magnetic resonance spectra of conductive ring-deuterated polyaniline consist of two peaks, one at the same chemical shift as the insulating form of the polymer and the second shifted by 5.8+/-1 ppm. The magnitude of the shift is field and temperature independent and is identified as a Knight shift. The deuterons undergoing a Knight shift originate from both the crystalline and amorphous regions of the sample, implying that conduction is mediated by delocalized polarons in both these regions. Spin count experiments demonstrate that in highly conductive samples, signal is lost not only by dephasing due to the proximity of localized unpaired electrons but also to high rf reflectance.

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Lead tetrakis(imidazolyl)borate solids: anion exchange, solvent intercalation, and self assembly of an organic anion.

The coordination polymer Pb[B(Im)(4)](NO(3))(xH(2)O), constructed by using sodium tetrakis(imidazolyl)borate and lead(II) nitrate solutions, is a layered material with the metal centers facing the interlayer spacing. As in naturally occurring layered minerals, this compound can readily undergo anion exchange and reversible intercalation of solvent water in the solid state with retention of crystallinity. We observed changes in solvent intercalation by (207)Pb solid state NMR (SSNMR) and thermogravimetric analysis (TGA). Stoichiometric exchange of (15)N nitrate for nitrate and iodide for nitrate is monitored by (15)N and (207)Pb SSNMR, and single crystals of the iodide-exchanged material Pb[B(Im)(4)]I were isolated. While the iodide compound can be obtained through facile exchange from the nitrate parent compound, the organic anion benzoate is placed in the interlayer spacing for nitrate under self-assembly conditions and forms an alternating monolayer in Pb[B(Im)(4)](C(6)H(5)COO)(0.5H(2)O). The ion exchange versus self-assembly behavior correlates with the structural differences in the three compounds. In both Pb[B(Im)(4)]I and Pb[B(Im)(4)](C(6)H(5)COO)(0.5H(2)O), the lead sites act as Lewis acids for the iodide and benzoate, respectively.

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Construction of a functional layered solid using the tetrakis(imidazolyl)borate coordinating anion.

The coordination polymer Pb[B(Im)(4)](NO(3)), constructed by using tetrakis(imidazolyl)borate and lead(II) nitrate solutions, is a layered material with the metal centers facing the interlayer spacing. As in naturally occurring layered minerals, this compound can readily undergo anion exchange in the solid state with retention of crystallinity. We examined stoichiometric exchange of (15)N-nitrate for nitrate and iodide for nitrate by (15)N and (207)Pb SSNMR and confirmed retention of crystallinity by IR and powder XRD diffraction.

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