Dynamic Hydrogen Disorder in Solid Tropolone. A Single-Crystal NMR Study of the Hydroxyl Deuterons

Detken, Andreas; Zimmermann, Herbert; Haeberlen, Ulrich; Luz, Z.

doi:10.1006/jmre.1997.1147

Cited by 14 publications

(6 citation statements)

References 7 publications

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“…From the NMR point of view, this stochastic modulation precludes from extracting the instantaneous interaction tensor linked to the minority and majority sites if the jump correlation time τ c is fast enough to completely average the tensor on the NMR time scale, that is when τ c is small compared to the inverse of the static line width (τ c Δ ≪ 1). Such a two-site jump model has been successful in interpreting the deuterium relaxation measurements in KDCO 3 in the low-temperature phase 31 and similar experiments in carboxylic acids 18,24-26 or other hydrogen-bond compounds . It is important to stress that such a two-site jump model does not make any hypothesis about the nature (classical or quantum) and the dimensionality of the multidimensional potential energy surface (MPES) describing the states of the two tautomers.…”

Section: Resultsmentioning

confidence: 99%

“…Such a two-site jump model has been successful in interpreting the deuterium relaxation measurements in KDCO 3 in the lowtemperature phase 31 and similar experiments in carboxylic acids 18,[24][25][26] or other hydrogen-bond compounds. 35 It is important to stress that such a two-site jump model does not make any hypothesis about the nature (classical or quantum) and the dimensionality of the multidimensional potential energy surface (MPES) describing the states of the two tautomers. This is a "two-pocket state" approximation of the real MPES.…”

Section: Resultsmentioning

confidence: 99%

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¹³C and ³⁹K High-Resolution Solid-State NMR Study of the Nonferroic Phase Transition of Potassium Hydrogen Carbonate. Complementarity between NMR and Incoherent Neutron Scattering

Odin

2004

J. Phys. Chem. B

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Potassium hydrogen carbonate KHCO 3 is formed of centrosymmetric dimers (HCO 3 -) 2 linked by hydrogen bonds, the protons being disordered in an asymmetric double-well potential at ambient temperature. This compound is a model for 0-dimensional hydrogen bonds. It undergoes a nonferroic nonferroelectric phase transition at T c ) 318 K, and the double-well potential becomes symmetric in the high-temperature phase. This phase transition is studied for the first time by variable-temperature 13 C and 39 K high-resolution solidstate NMR experiments. We present an original method to correlate NMR data to other local probes such as incoherent neutron scattering experiments to extract structural information from powder NMR experiments. Using this method, the eigenvalues and jump angle of the chemical shift tensor of the carbon 13 C and the quadrupolar interaction of the potassium 39 K could be extracted in the completely ordered phase, and their evolution with temperature is correlated to the proton-dynamic disorder within the hydrogen bond. This study also illustrates the complementarity between NMR and incoherent neutron-scattering experiments in the study of hydrogen bonding.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

¹³C and ³⁹K High-Resolution Solid-State NMR Study of the Nonferroic Phase Transition of Potassium Hydrogen Carbonate. Complementarity between NMR and Incoherent Neutron Scattering

Odin

2004

J. Phys. Chem. B

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“…In the solid state, for example, asymmetric hydrogen bonds in a centrosymmetric environment have been observed, while, with a second system, a distortion of local symmetry caused by dynamic hydrogen bonding effects was thought to be the cause of peak splitting in 13C CPMAS spectra . In solid tropolone, dynamic hydrogen bonds were shown to provide an efficient NMR relaxation mechanism, while, with proton sponges, structural and NMR studies suggest that asymmetric hydrogen bonding with a shallow double-minimum potential well is the norm for these systems.…”

Section: Resultsmentioning

confidence: 99%

Solid-State Changes in Ligand-to-Metal Charge-Transfer Spectra of (NH₃)₅Ru^III(2,4-dihydroxybenzoate) and (NH₃)₅Ru^III(xanthine) Chromophores

et al. 2008

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Five distorted-octahedral complexes containing (NH3)5Ru(III)L ions, where L = 2,4-dihydroxybenzoate or a xanthine, have been studied using a combination of X-ray crystallography, solution and polarized single-crystal electronic absorption spectroscopy, and first principles electronic structure computational techniques. Both yellow (2) and red (3) forms of the complex (NH3)5Ru(III)L, where L = 2,4-dihydroxybenzoate, as well as three xanthine complexes in which L = hypoxanthine-kappaN(7) (4), 7-methylhypoxanthine-kappaN(9) (5), and 1,3,9-trimethylxanthine-kappaN(7) (6) were examined. In the solid state, some of these complexes exhibit split low-energy ligand-to-metal charge-transfer (LMCT) bands. Traditional solid-state effects, such as ligand pi-pi overlap or hydrogen bonding that might lead to splitting of electronic absorption bands, were probed in an attempt to identify the origins of these unusual observations. For comparison, companion studies were carried out for spectroscopically normal reference complexes of the same ligands. Time-dependent density-functional theory (TD-DFT) calculations, employing modified B3LYP-type functionals with increased contributions of exact exchange, attribute the color change in the crystalline complexes 2 and 3 to pi(ligand) --> Ru[d(pi)] LMCT bands which, in the red form (3), arise from ligand donor pi-orbitals split by strongly overlapping phenyl moieties in centrosymmetric (NH3)5Ru(III)(2,4-dihydroxybenzoate) dimers. Complex 5 does not show split visible absorptions, whereas both the polarizations and energies of the split visible absorptions shown by 4 and 6 also suggest assignment as LMCT. No support is found for relating the split absorptions of 4 and 6 to the details of pi-pi xanthine overlap in the solid state; indeed, complex 4 enjoys considerably less pi-stacking overlap than does 5. We feel compelled to attribute the split absorptions in crystalline 4 and 6 to the emergence of a LMCT transition originating in the carbonyl lone pair, potentially deriving intensity from the significant intramolecular N-H...O hydrogen bonding present in both 4 and 6 (but not in 5). The electronic structure calculations suggest an O(n) --> Ru[d(sigma*)] LMCT transition; however, this novel assignment must be considered tentative.

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“…These results are intriguing; unfortunately, because the intermolecular hydrogen bond in systems of this sort is serendipitiously dependent on crystal packing, it is difficult systematically to pursue this avenue of research. In contrast, intramolecular hydrogen bonds, such as those observed previously by NMR in benzoylacetone [8], tropolone [9], and a host of other systems, can be 'tuned' by varying the steric bulk of substituent groups. The availability of a series of substituted cyanomalonaldehydes, synthesized originally as ligands for lanthanide ions, affords the opportunity to study the deuterium electric field gradient systematically as a function of molecular geometry.…”

Section: Introductionmentioning

confidence: 85%

Deuterium NMR and Ab Initio Studies of Strongly Hydrogen-Bonded Molecules

Zhao

Dvorak

Silvernail

et al. 2002

Solid State Nuclear Magnetic Resonance

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Dynamic Hydrogen Disorder in Solid Tropolone. A Single-Crystal NMR Study of the Hydroxyl Deuterons

Cited by 14 publications

References 7 publications

¹³C and ³⁹K High-Resolution Solid-State NMR Study of the Nonferroic Phase Transition of Potassium Hydrogen Carbonate. Complementarity between NMR and Incoherent Neutron Scattering

¹³C and ³⁹K High-Resolution Solid-State NMR Study of the Nonferroic Phase Transition of Potassium Hydrogen Carbonate. Complementarity between NMR and Incoherent Neutron Scattering

Solid-State Changes in Ligand-to-Metal Charge-Transfer Spectra of (NH₃)₅Ru^III(2,4-dihydroxybenzoate) and (NH₃)₅Ru^III(xanthine) Chromophores

Deuterium NMR and Ab Initio Studies of Strongly Hydrogen-Bonded Molecules

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Dynamic Hydrogen Disorder in Solid Tropolone. A Single-Crystal NMR Study of the Hydroxyl Deuterons

Cited by 14 publications

References 7 publications

13C and 39K High-Resolution Solid-State NMR Study of the Nonferroic Phase Transition of Potassium Hydrogen Carbonate. Complementarity between NMR and Incoherent Neutron Scattering

13C and 39K High-Resolution Solid-State NMR Study of the Nonferroic Phase Transition of Potassium Hydrogen Carbonate. Complementarity between NMR and Incoherent Neutron Scattering

Solid-State Changes in Ligand-to-Metal Charge-Transfer Spectra of (NH3)5RuIII(2,4-dihydroxybenzoate) and (NH3)5RuIII(xanthine) Chromophores

Deuterium NMR and Ab Initio Studies of Strongly Hydrogen-Bonded Molecules

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¹³C and ³⁹K High-Resolution Solid-State NMR Study of the Nonferroic Phase Transition of Potassium Hydrogen Carbonate. Complementarity between NMR and Incoherent Neutron Scattering

¹³C and ³⁹K High-Resolution Solid-State NMR Study of the Nonferroic Phase Transition of Potassium Hydrogen Carbonate. Complementarity between NMR and Incoherent Neutron Scattering

Solid-State Changes in Ligand-to-Metal Charge-Transfer Spectra of (NH₃)₅Ru^III(2,4-dihydroxybenzoate) and (NH₃)₅Ru^III(xanthine) Chromophores