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Chemical Structure| 319-88-0 Chemical Structure| 319-88-0

Structure of 319-88-0

Chemical Structure| 319-88-0

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Gunaga, Shubha S. ; Bryce, David L. ;

Abstract: Dynamic processes are responsible for the functionality of a range of materials, biomols., and catalysts. We report a detailed systematic study of the modulation of Me rotational dynamics via the direct and the indirect influence of noncovalent halogen bonds. For this purpose, a novel series of cocryst. architectures featuring halogen bonds (XB) to tetramethylpyrazine (TMP) is designed and prepared using gas-phase, solution, and solid-state mechanochem. methods. Single-crystal X-ray diffraction reveals the capacity of mol. bromine as well as weak chloro-XB donors to act as robust directional structure-directing elements. Me rotational barriers (Ea) measured using variable-temperature deuterium solid-state NMR range from 3.75 ± 0.04 kJ mol-1 in 1,3,5-trichloro-2,4,6-trifluorobenzene·TMP to 7.08 ± 0.15 kJ mol-1 in 1,4-dichlorotetrafluorobenzene·TMP. Ea data for a larger series of TMP cocrystals featuring chloro-, bromo-, and iodo-XB donors are shown to be governed by a combination of steric and electronic factors. The average number of carbon-carbon close contacts to the Me group is found to be a key steric metric capable of rationalizing the observed trends within each of the Cl, Br, and I series. Differences between each series are accounted for by considering the strength of the σ-hole on the XB donor. One possible route to modulating dynamics is therefore via designer cocrystals of variable stoichiometry, maintaining the core chem. features of interest between a given donor and acceptor while simultaneously modifying the number of carbon close contacts affecting dynamics. These principles may provide design opportunities to modulate more complex geared or cascade dynamics involving larger functional groups.

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Product Details of [ 319-88-0 ]

CAS No. :319-88-0
Formula : C6Cl3F3
M.W : 235.42
SMILES Code : FC1=C(Cl)C(F)=C(Cl)C(F)=C1Cl
MDL No. :MFCD00000587

Safety of [ 319-88-0 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P264-P271-P280-P302+P352-P304+P340+P312-P305+P351+P338-P332+P313-P337+P313-P362-P403+P233-P501

Application In Synthesis of [ 319-88-0 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

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