“Long-distance” H/D isotopic self-organization phenomena in scope of the infrared spectra of hydrogen-bonded terephthalic and phthalic acid crystals

Flakus, Henryk T.; Hachuła, Barbara; Hołaj-Krzak, Jakub T.; Al-Agel, F.A.; Rekik, Najeh

doi:10.1016/j.saa.2016.08.051

Cited by 15 publications

(16 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Stretching vibrations of H-bonds have a high diagnostic value for determination of the nature and strength of these bonds [ 97 , 98 ]. Previously, the spectral manifestations of dimerization and isotopic effects on spectroscopic observables were studied for different molecular systems [ 99 , 100 , 101 , 102 , 103 , 104 , 105 , 106 , 107 , 108 ] including carboxylic acid dimers [ 109 , 110 ]. Upon carboxylic acid dimerization, the structure of the OH stretching band in IR spectra changes most prominently: The narrow band of monomers changes to a broad, intensive, and complex substructured band of dimers shifted to lower wavenumbers.…”

Section: Resultsmentioning

confidence: 99%

Inter- vs. Intramolecular Hydrogen Bond Patterns and Proton Dynamics in Nitrophthalic Acid Associates

et al. 2020

View full text Add to dashboard Cite

Noncovalent interactions are among the main tools of molecular engineering. Rational molecular design requires knowledge about a result of interplay between given structural moieties within a given phase state. We herein report a study of intra- and intermolecular interactions of 3-nitrophthalic and 4-nitrophthalic acids in the gas, liquid, and solid phases. A combination of the Infrared, Raman, Nuclear Magnetic Resonance, and Incoherent Inelastic Neutron Scattering spectroscopies and the Car–Parrinello Molecular Dynamics and Density Functional Theory calculations was used. This integrated approach made it possible to assess the balance of repulsive and attractive intramolecular interactions between adjacent carboxyl groups as well as to study the dependence of this balance on steric confinement and the effect of this balance on intermolecular interactions of the carboxyl groups.

show abstract

Section: Resultsmentioning

confidence: 99%

Inter- vs. Intramolecular Hydrogen Bond Patterns and Proton Dynamics in Nitrophthalic Acid Associates

et al. 2020

View full text Add to dashboard Cite

show abstract

“…In the particular situations dealing with the succinic acid associations, 25,31 it was evinced qualitatively on the basis of the obtained infrared spectra that the coplanarity of molecules favors the adjacent cycles of carboxyl groups to be coupled, suggesting thereby that the mutual orientation of the atoms is not the unique mechanism for evaluating the strength of hydrogen bonds. 25,32 As can be seen from the theoretical results provided in Table 5, the dimerization of SA molecules is basically not accompanied by the variation of the geometry of the h 6 variant molecules in relation to the monomeric model structure, resulting from the formation of hydrogen bridges, i.e., within the H…”

Section: Effects Of Isotopicmentioning

confidence: 95%

“…It has also been proved that the presence of deuterons, apart from hydrogen bridges, cannot be neglected on the physicochemical and spectral features of terephthalic acid, unlike the situation dealing with succinic acid crystals. 25,31,32 In the context of outlined infrared spectral properties of terephthalic acid crystals, it is important to draw attention to the heterocyclic associations in monocarboxylic acids. 17 In order to interpret the diverse spectral comportments of structurally similar molecular systems, we propose distinct mechanisms of interactions of the associated molecules involved in hydrogen bonds.…”

Section: Introductionmentioning

confidence: 99%

Elucidating the Infrared Spectral Properties of Succinic Molecular Acid Crystals: Illustration of the Structure and the Hydrogen Bond Energies of the Crystal and Its Deuterated Analogs

et al. 2022

Self Cite

View full text Add to dashboard Cite

Herein, the infrared spectroscopic properties of molecular succinic acid crystals (SA) and their four isotopic analogs [C 2 H 4 (COOH) 2 , h 6 -SA; C 2 H 4 (COOD) 2 , d 2 -SA; C 2 D 4 (COOH) 2 , d 4 -SA; C 2 D 4 (COOD) 2 , d 6 -SA] are reported. The correlation between the structure of succinic acid molecules and their corresponding hydrogen bond energies is elucidated. The effects related to the isotopic dilution as well as the changes in the spectrum recording temperature on the fine structures of the v O−H and v O−D bands are interpreted. The infrared spectral anomalies detected in the spectra of isotopically neat succinic nanocrystal acids are confirmed by theoretical calculations using density functional theory (DFT). According to previous spectroscopic studies of succinic acid and those carried out for α,ω-dicarboxylic acids, a decent agreement between the experimental results and the theoretical DFT simulations is obtained. Moreover, the spectra of single crystals of the h 6 and d 4 succinic acid variants prove that the vibrational coupling mechanism between the (COOH) 2 cycles is rigorously convergent to that detected in the spectra of aromatic carboxylic acids, suggesting thereby that the promotion of symmetryforbidden high stretching IR transitions plays a crucial role. Furthermore, the obtained experimental results reveal that the succinic acid shows a spectral behavior significantly different from that characteristic of hydrogen associations of other acids of homologous series, such as the glutaric, adipic, malonic, and pimelic acid crystals. The results obtained herein shed light on the way to explore the revealed structure of isotopic derivatives of succinic acid crystals and may prove to be useful results for understanding the nature of unconventional interactions as well as the macroscopic energy effects directing the development of hydrogen associations.

show abstract

“…In doing so, the ν(CH) Raman signals become ν(CD) signals, which, in the case of ZTA1 for example, corresponds to a shift of the stretching vibrations from at 3064 and 3105 cm -1 to 2287 and 2321 cm -1 (see ESI Figure S19). [95] Therefore, isotope labelling by deuteration can be seen as a way of shifting Raman vibrations in an area of the spectrum were no signal from the jar is expected, allowing a more straightforward observation of the evolving vibration modes as well as an easier post-synthesis data treatment. Both methods, using D2O or d4-BDC, can also be combined in order to study the change of kinetics for such reactions.…”

Section: O Nmr Analyses Of Carboxylate and Hydroxyl Binding Modes In Zn-bdc Structuresmentioning

confidence: 99%

From operando Raman mechanochemistry to "NMR crystallography": understanding the structures and interconversion of Zn-terephthalate networks using selective 17O-labelling.

Leroy

Métro

Hung

et al. 2022

Preprint

View full text Add to dashboard Cite

The description of the formation, structure and reactivity of coordination networks and MOFs remains a real challenge in a number of cases. This is notably true for compounds composed of Zn2+ ions and terephthalate ligands (benzene 1,4-dicarboxylate, BDC), because of the difficulties in isolating them as pure phases and/or because of the presence of structural defects. Here, using mechanochemistry in combination with operando Raman spectroscopy, the observation of the formation of various zinc-terephthalate compounds was rendered possible, allowing the distinction and isolation of three intermediates during the ball-milling synthesis of Zn3(OH)4(BDC). An “NMR crystallography” approach was then used, combining solid-state NMR (1H, 13C and 17O) and DFT calculations, in order to refine the poorly described crystallographic structures of these phases. Particularly noteworthy are the high-resolution 17O NMR analyses, which were made possible in a highly efficient and cost-effective way, thanks to the selective 17O-enrichment of either hydroxyl or terephthalate groups by ball-milling. This allowed the presence of defect sites to be identified for the first time in one of the phases, and the nature of the H-bonding network of the hydroxyls to be established in another. Lastly, the possibility of using deuterated precursors (e.g. D2O and d4-BDC) during ball-milling is also introduced, as a means for observing specific transformations during operando Raman spectroscopy studies, that would not have been possible with hydrogenated equivalents. Overall, the synthetic and spectroscopic approaches developed herein are expected to push forward the understanding of the structure and reactivity of other complex coordination networks and MOFs.

show abstract

“Long-distance” H/D isotopic self-organization phenomena in scope of the infrared spectra of hydrogen-bonded terephthalic and phthalic acid crystals

Cited by 15 publications

References 50 publications

Inter- vs. Intramolecular Hydrogen Bond Patterns and Proton Dynamics in Nitrophthalic Acid Associates

Inter- vs. Intramolecular Hydrogen Bond Patterns and Proton Dynamics in Nitrophthalic Acid Associates

Elucidating the Infrared Spectral Properties of Succinic Molecular Acid Crystals: Illustration of the Structure and the Hydrogen Bond Energies of the Crystal and Its Deuterated Analogs

From operando Raman mechanochemistry to "NMR crystallography": understanding the structures and interconversion of Zn-terephthalate networks using selective 17O-labelling.

Contact Info

Product

Resources

About