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Supramolecular Structure of Phenyl Derivatives of Butanol Isomers.

ABSTRACT: Wide-angle X-ray scattering patterns were recorded for a series of aliphatic butanol isomers (n-, iso-, sec-, tert-butanol) and their phenyl derivatives (4-phenyl-1-butanol, 2-methyl-3-phenyl-1-propanol, 4-phenyl-2-butanol, and 2-methyl-1-phenyl-2-propanol, respectively) to determine their atomic-scale structure with particular emphasis on the formation of supramolecular clusters. In addition, molecular dynamics simulations were carried out and yielded good agreement with experimental data. The combination of experimental and theoretical results allowed clarification of the origin of the pre-peak appearing at low scattering angles for the aliphatic butanols and its absence for their phenyl counterparts. It was demonstrated that the location of the hydroxyl group in the molecule of alkyl butanol, its geometry, and rigidity determine the morphology of the supramolecular clusters, while the addition of the aromatic moiety causes more disordered organization of molecules. The phenyl group significantly decreases the number of hydrogen bonds and size of the supramolecular clusters formed via the O-H···O scheme. The lower association ability of phenyl alcohols via H-bonds is additionally attenuated by the appearance of competing π-π configurations evidenced by the structural models.

SUBMITTER: Grelska J

PROVIDER: S-EPMC9125557 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Supramolecular Structure of Phenyl Derivatives of Butanol Isomers.

Grelska Joanna J Jurkiewicz Karolina K Burian Andrzej A Pawlus Sebastian S

The journal of physical chemistry. B 20220506 19

Wide-angle X-ray scattering patterns were recorded for a series of aliphatic butanol isomers (n-, iso-, sec-, tert-butanol) and their phenyl derivatives (4-phenyl-1-butanol, 2-methyl-3-phenyl-1-propanol, 4-phenyl-2-butanol, and 2-methyl-1-phenyl-2-propanol, respectively) to determine their atomic-scale structure with particular emphasis on the formation of supramolecular clusters. In addition, molecular dynamics simulations were carried out and yielded good agreement ...[more]

PMID: 35522735

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Project description:The Waddington mechanism, or the Waddington-type reaction pathway, is crucial for low-temperature oxidation of both alkenes and alcohols. In this study, the Waddington mechanism in the oxidation chemistry of butene and butanol isomers was systematically investigated. Fundamental quantum chemical calculations were conducted for the rate constants and thermodynamic properties of the reactions and species in this mechanism. Calculations were performed using two different ab initio solvers: Gaussian 09 and Orca 4.0.0, and two different kinetic solvers: PAPR and MultiWell, comprehensively. Temperature- and pressure-dependent rate constants were performed based on the transition state theory, associated with the Rice Ramsperger Kassel Marcus and master equation theories. Temperature-dependent thermochemistry (enthalpies of formation, entropy, and heat capacity) of all major species was also conducted, based on the statistical thermodynamics. Of the two types of reaction, dissociation reactions were significantly faster than isomerization reactions, while the rate constants of both reactions converged toward higher temperatures. In comparison, between two ab initio solvers, the barrier height difference among all isomerization and dissociation reactions was about 2 and 0.5 kcal/mol, respectively, resulting in less than 50%, and a factor of 2-10 differences for the predicted rate coefficients of the two reaction types, respectively. Comparing the two kinetic solvers, the rate constants of the isomerization reactions showed less than a 32% difference, while the rate of one dissociation reaction (P1 ↔ WDT12) exhibited 1-2 orders of magnitude discrepancy. Compared with results from the literature, both reaction rate coefficients (R4 and R5 reaction systems) and species' thermochemistry (all closed shell molecules and open shell radicals R4 and R5) showed good agreement with the corresponding values obtained from the literature. All calculated results can be directly used for the chemical kinetic model development of butene and butanol isomer oxidation.

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Supramolecular Structure of Phenyl Derivatives of Butanol Isomers.

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Supramolecular Structure of Phenyl Derivatives of Butanol Isomers.

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