Fine-Tuning the Motion of Tetrafluoro-1,4-Benzoquinone Within Charge-Transfer Cocrystals Through Variation of the Donor: An Entropic and Enthalpic Point of View
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00637700" target="_blank" >RIV/61388963:_____/25:00637700 - isvavai.cz</a>
Result on the web
<a href="https://doi.org/10.1002/chem.202501275" target="_blank" >https://doi.org/10.1002/chem.202501275</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/chem.202501275" target="_blank" >10.1002/chem.202501275</a>
Alternative languages
Result language
angličtina
Original language name
Fine-Tuning the Motion of Tetrafluoro-1,4-Benzoquinone Within Charge-Transfer Cocrystals Through Variation of the Donor: An Entropic and Enthalpic Point of View
Original language description
In this work, we report a detailed investigation on the factors affecting the in-plane motion of tetrafluoro-1,4-benzoquinone (TFBQ) within a series of charge-transfer (CT) cocrystals formed with various fused aromatic donors. Six crystalline materials were obtained, including four cocrystals, a polymorph, and a solid solution. These were characterized by single-crystal X-ray diffraction (SC XRD), solid-state NMR, FTIR, UV-Vis spectroscopy, and DFT calculations. All cocrystals exhibited short pi-stacking interactions and varied noncovalent interactions (NCI) modulating the in-plane motion of TFBQ. 19F T-1 relaxation measurements allowed the quantification of the activation enthalpies (Delta H double dagger) and entropies (Delta S double dagger), with theoretical calculations backing these results. Cocrystal 4 is the solid with the most restricted motions due to the presence of strong hydrogen bonds. In contrast, cocrystal 3a depicts the highest in-plane motional frequencies (up to 2.2 MHz at 300 K), owing to the weak contacts around TFBQ. Surprisingly, a solid solution (5), which resembled a mixture of cocrystals 2 and 3a, displayed no significant in-plane motions, despite having similar packing and relaxation behavior to the binary cocrystals. This work illustrates how subtle variations in donor structure affect the in-plane motions and photophysical properties of CT cocrystals, providing valuable insight into the rational design of functional materials.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/LUC24101" target="_blank" >LUC24101: NMR Crystallography of Molecular Solids</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Chemistry - A European Journal
ISSN
0947-6539
e-ISSN
1521-3765
Volume of the periodical
31
Issue of the periodical within the volume
42
Country of publishing house
DE - GERMANY
Number of pages
11
Pages from-to
e202501275
UT code for WoS article
001497404000001
EID of the result in the Scopus database
2-s2.0-105006798741