Topological insights into the 1/1 diacetyl/water complex gained using a new methodological approach

Dargent, D.; Zins, Emilie‐Laure; Madebène, Bruno; Alikhani, M. E.

doi:10.1007/s00894-015-2751-9

Cited by 8 publications

(9 citation statements)

References 80 publications

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“…In a recent theoretical paper about 1/1 DAC/H 2 O complex 12 we have shown that the analysis of monomers realized with the combination of topological tools, mainly MESP, ELF and QTAIM allowed identifying favorable interaction sites to predict 1/1 structures. Three isomers have been characterized, namely S 1 , S 2 and S 3 , and their structures optimized at the MP2/AVTZ level of theory are reported in Figure 1.…”

Section: Iii-1 Theoretical Resultsmentioning

confidence: 99%

“…It has been shown in many previous solid 8 and gas phase studies [9][10][11] that very different structural architectures of hydrated organic 2 M/H 2 O clusters could be obtained, depending on the nature of the organic molecule M involved. The objective of the present work is to characterize by a combined experimental and theoretical approach the first step of hydration of an organic molecule M. In a recent paper 12 , a six-step methodological approach aiming at characterizing the conformational landscape of mono-hydrated 1/1 M/H 2 O isomers emphasized the value of topological methods to evidence the most stable isomers. We selected the small centro-symmetric diacetyl molecule (C 4 H 6 O 2 , DAC) as partner of the hydration process.…”

Section: -Introductionmentioning

confidence: 99%

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Conformational Landscape of the 1/1 Diacetyl/Water Complex Investigated by Infrared Spectroscopy and ab Initio Calculations

et al. 2016

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The complexes of diacetyl with water have been studied experimentally by Fourier transform infrared (FTIR) spectroscopy coupled to solid neon matrix and supersonic jet, and anharmonic ab initio calculations. The vibrational analysis of neon matrix spectra over the 100-7500 cm -1 infrared range confirms the existence of two nearly isoenergetic one-to-one(1/1) diacetyl-water S 1 and S 2 isomers already evidenced in a previous argon matrix study. A third form (S 3 ) predicted slightly less stable [D. Dargent et al. , J. Mol. Mod. 21, 214 (2015)] is not observed. The correct agreement obtained between neon matrix and anharmonic calculated vibrational frequencies is exploited in several cases to derive band assignments for the vibrational modes of a specific isomer. Thereafter, theoretical x ij anharmonic coupling constants are used for the attribution of combination bands and overtones relative to the 1/1 dimer. Finally, the most stable isomer of the one-to-two (1/2) diacetyl-water complex is identified in the OH stretching region of water on the grounds of comparison of experimental and calculated vibrational shifts between water dimer and the three most stable 1/2 isomers. I -IntroductionIt is now well established that non-covalent interactions such as hydrogen bonds involved in small hydrated clusters play an essential role in atmospheric chemistry, astrophysics and also in many biochemical and catalytic processes.1 Since the pioneering spectroscopic works about the enthalpy and the hydrogen bridges in crystallographic structures such as ice and liquid water, 2,3 many advanced experimental methods were developed in the last thirty years to interpret the bulk water structure and dynamics. In this context, the spectroscopic study of small water clusters produced at very low temperature in nearly isolated conditions proved to be determinant for improving the building of reliable intermolecular potential energy surfaces based on a back and forth procedure between experiment and theory. As a first step toward this objective, we can cite the challenging studies based on jet-cooled far-and near-IR laser and microwave spectroscopy which yielded new insights into the tunneling motions of the water dimer 4-6 and allowed to determine a polarisable water pair potential. 7The huge capacity of water to establish hydrogen bonds with the close environment owing to its twice role of hydrogen-bond donor and acceptor would suggest to use a molecular approach based on a step by step increase of the size of hydrates for most studies related to the hydration process of organic species. It has been shown in many previous solid 8 and gas phase studies 9-11 that very different structural architectures of hydrated organic In the following we reported a series of experiments mainly achieved in solid neon and at a least degree in the supersonic expansion of the Jet-AILES facility on the infrared beamline of the SOLEIL synchrotron. Previous studies realized in our group about the characterization of small hydrated complexes highlight...

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Section: Iii-1 Theoretical Resultsmentioning

confidence: 99%

Section: -Introductionmentioning

confidence: 99%

Conformational Landscape of the 1/1 Diacetyl/Water Complex Investigated by Infrared Spectroscopy and ab Initio Calculations

et al. 2016

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“…The MESP is found to be a powerful tool for studying molecular surfaces . In this study, the MESP calculations demonstrated the negative potential at cyclopropane bonds which is responsible for the interaction with electropositive Li + ions.…”

Section: Resultsmentioning

confidence: 63%

“…The MESP is found to be a powerful tool for studying molecular surfaces. [58][59][60] In this study, the MESP calculations demonstrated the negative potential at cyclopropane bonds which is responsible for the interaction with electropositive Li + ions. The change in V min values upon addition of each Li + ion indicates the depletion of electron density on other cyclopropane bonds.…”

Section: Molecular Electrostatic Potential Study (Mesp)mentioning

confidence: 57%

Probing the bent bonds in cyclopropane systems for gas storage and separation process: A computational study

Wakchaure

Ganguly

2020

J Comput Chem

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The hydrogen, carbon dioxide, and carbon monoxide gas adsorption and storage capacity of lithium‐decorated cyclopropane ring systems were examined with quantum chemical calculations at density functional theory, DFT M06‐2X functional using 6‐31G(d) and cc‐pVDZ basis sets. To examine the reliability of M06‐2X DFT functional, a few representative systems are also examined with complete basis set CBS‐QB3 method and CCSD‐aug‐cc‐pVTZ level of theory. The cyclopropane systems can bind to one Li+ ion; however, the corresponding the methylated systems can bind with two Li+ ions. The cyclopropane systems can adsorb six hydrogen molecules with an average binding energy of 3.8 kcal/mol. The binding free energy (ΔG) values suggest that the hydrogen adsorption process is feasible at 273.15 K. The calculation of desorption energies indicates the recyclable property of gas adsorbed complexes. The same number of CO2 and CO gas molecules can also be adsorbed with an average binding energy of −14.4 kcal/mol and −10.7 kcal/mol, respectively. The carbon dioxide showed ~3–4 kcal/mol better binding energy as compared to carbon monoxide and hence such designed systems can function as a potential candidate for the separation of these flue gas molecules. The nature of interactions in complexes was examined with atoms in molecules analysis revealed the electrostatic nature for the interaction of Li+ ion with cyclopropane rings. The chemical hardness and electrophilicity calculations showed that the gas adsorbed complexes are rigid and therefore robust as gas storage materials.

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“…Additionally, this well-established tool is efficient in understanding various chemical properties like chemical reactivity, intermolecular interactions and inductive effects, etc. (Dargent et al, 2015). The most negative (V min , red region) and positive (V max , blue region) electrostatic potential value in MESP indicate the electron donating and accepting tendency in a particular molecule, respectively (Matta, 2014).…”

Section: Molecular Electrostatic Potential Surfacementioning

confidence: 99%

Molecular Structure, Spectral Investigations, Hydrogen Bonding Interactions and Reactivity-Property Relationship of Caffeine-Citric Acid Cocrystal by Experimental and DFT Approach

Verma

Srivastava

Srivastava³

et al. 2021

Front. Chem.

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The pharmaceutical cocrystal of caffeine-citric acid (CAF-CA, Form II) has been studied to explore the presence of hydrogen bonding interactions and structure-reactivity-property relationship between the two constituents CAF and Citric acid. The cocrystal was prepared by slurry crystallization. Powder X-ray diffraction (PXRD) analysis was done to characterize CAF-CA cocrystal. Also, differential scanning calorimetry (DSC) confirmed the existence of CAF-CA cocrystal. The vibrational spectroscopic (FT-IR and FT-Raman) signatures and quantum chemical approach have been used as a strategy to get insights into structural and spectral features of CAF-CA cocrystal. There was a good correlation among the experimental and theoretical results of dimer of cocrystal, as this model is capable of covering all nearest possible interactions present in the crystal structure of cocrystal. The spectroscopic results confirmed that (O33-H34) mode forms an intramolecular (C25 = O28∙∙∙H34-O33), while (O26-H27) (O39-H40) and (O43-H44) groups form intermolecular hydrogen bonding (O26-H27∙∙∙N24-C22, O39-H40∙∙∙O52 = C51 and O43-H44∙∙∙O86 = C83) in cocrystal due to red shifting and increment in bond length. The quantum theory of atoms in molecules (QTAIM) analysis revealed (O88-H89∙∙∙O41) as strongest intermolecular hydrogen bonding interaction with interaction energy −12.4247 kcal mol−1 in CAF-CA cocrystal. The natural bond orbital analysis of the second-order theory of the Fock matrix highlighted the presence of strong interactions (N∙∙∙H and O∙∙∙H) in cocrystal. The HOMO-LUMO energy gap value shows that the CAF-CA cocrystal is more reactive, less stable and softer than CAF active pharmaceutical ingredients. The electrophilic and nucleophilic reactivities of atomic sites involved in intermolecular hydrogen bond interactions in cocrystal have been demonstrated by mapping electron density isosurfaces over electrostatic potential i.e. plotting molecular electrostatic potential (MESP) map. The molar refractivity value of cocrystal lies within the set range by Lipinski and hence it may be used as orally active form. The results show that the physicochemical properties of CAF-CA cocrystal are enhanced in comparison to CAF (API).

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Topological insights into the 1/1 diacetyl/water complex gained using a new methodological approach

Cited by 8 publications

References 80 publications

Conformational Landscape of the 1/1 Diacetyl/Water Complex Investigated by Infrared Spectroscopy and ab Initio Calculations

Conformational Landscape of the 1/1 Diacetyl/Water Complex Investigated by Infrared Spectroscopy and ab Initio Calculations

Probing the bent bonds in cyclopropane systems for gas storage and separation process: A computational study

Molecular Structure, Spectral Investigations, Hydrogen Bonding Interactions and Reactivity-Property Relationship of Caffeine-Citric Acid Cocrystal by Experimental and DFT Approach

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