Stabilizing a cis viologen via co-crystal engineering: electric and magnetic fields are in action to confirm no π-mer formation

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00639599" target="_blank" >RIV/61388963:_____/25:00639599 - isvavai.cz</a>

Result on the web

<a href="https://doi.org/10.1039/D5TC02137E" target="_blank" >https://doi.org/10.1039/D5TC02137E</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d5tc02137e" target="_blank" >10.1039/d5tc02137e</a>

Result language

angličtina

Original language name

Stabilizing a cis viologen via co-crystal engineering: electric and magnetic fields are in action to confirm no π-mer formation

Original language description

Stabilizing a cis isomer is challenging due to the higher energy barrier than the trans isomer. However, external stimuli can cross this energy barrier to achieve the cis isomer. We report conformationally modulated electrical conductivity in anthracene-substituted viologen dications (1,1′-disubstituted-4,4′-bipyridinium salts, V2+·2X−). The AnV2+ adopts either a trans or cis conformation, the latter stabilized through non-covalent interactions with dimethylamine (DMA). While solution-state AnV2+ exhibits rapid rotation about the methylene linker, single-crystal X-ray diffraction confirms distinct packing modes for cis and trans conformers. Two-terminal electronic devices, ITO/AnV2+/ITO prepared from respective crystal forms, exhibit dramatically different charge transport properties, with the trans-AnV2+ showing a 33-fold higher electrical conductivity, which was further supported by relatively higher activation energy needed for cis than trans isomer (129.4 meV vs. 102.5 meV). Computational studies corroborate the thermodynamic stability of the trans form in the absence of DMA, and periodic DFT reveals that DMA inclusion stabilizes the cis crystal. External and varied magnetic fields applied during electrical measurements further confirm that viologens remain in the native dicationic state. Our present study on tuning electrical conductivity in cis and trans viologens emphasizes the importance of solid-state molecular conformation in designing organic electronic materials for nanofabrication towards practical applications.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

—

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2025

Confidentiality

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

Name of the periodical

Journal of Materials Chemistry C

ISSN

2050-7526

e-ISSN

2050-7534

Volume of the periodical

13

Issue of the periodical within the volume

38

Country of publishing house

GB - UNITED KINGDOM

Number of pages

13

Pages from-to

19829-19841

UT code for WoS article

001562799500001

EID of the result in the Scopus database

2-s2.0-105017596056