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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/LUC24101" target="_blank" >LUC24101: NMR krystalografie molekulárních pevných látek</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

1521-3765

Svazek periodika

31

Číslo periodika v rámci svazku

42

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

11

Strana od-do

e202501275

Kód UT WoS článku

001497404000001

EID výsledku v databázi Scopus

2-s2.0-105006798741