Stacking for success: Controlling molecular order in a new zwitterionic system for organic electronics

Stacking for success: Controlling molecular order in a new zwitterionic system for organic electronics Full article

Journal

Journal of Molecular Structure
ISSN: 0022-2860

Output data

Year: 2026, Volume: 1372, Article number : 146637, Pages count : 13 DOI: 10.1016/j.molstruc.2026.146637

Tags

Zwitterionic compounds; Crystal engineering; π–π stacking; Counter-ion effect; Hydrogen bonding; Charge transport

Authors

Norkov S.V. ¹ , Makarov S.G. ¹ , Travkin V.V. ² , Baranov E.V. ¹ , Fukin G.K. ¹ , Romanenko G.V. ³ , Kuropatov V.A. ¹

Affiliations

1	G. A. Razuvaev Institute of Organometallic Chemistry of the Russian Academy of Sciences, Russian Federation, 603950 Box-445, Nizhny Novgorod, Tropinina St., 49
2	Institute for Physics of Microstructures of the Russian Academy of Sciences (IPM RAS) GSP-105, Nizhny Novgorod, 603950 Russia
3	International Tomography Center of Siberian Branch of RAS, 3a Institutskaya Str, Novosibirsk 630090, Russia

The performance of organic optoelectronic devices is critically dependent on the supramolecular organization of functional interface materials. Here we report the synthesis of a new zwitterionic compound 4 based on a 2-aryl-1,3-dithiolium-fused benzodioxolene core and a series of its organic salts with bromide (5), perchlorate (6), and triiodide (7) counterions. Single-crystal X-ray diffraction demonstrates that counter-ion nature and stoichiometry are the primary determinants of molecular packing: whereas simple salts 5 and 6 are governed by hydrogen bonding, the mixed co-crystalline compound 8 combines strong O–H···O hydrogen bonds with well-defined π–π stacking and an isolated triiodide sublattice. TD-DFT calculations reveal that the hydrogen-bonded cation–zwitterion dimer in 8 exhibits a pronounced intermolecular charge-transfer excited state, consistent with photoinduced carrier generation. Accordingly, thin-film conductivity measurements show that 8 achieves the highest dark conductivity (σ = 6 × 10⁻⁸ S/cm) and photosensitivity (ΔSph = 1.0) in the series — up to three orders of magnitude above the neat zwitterion 4. The findings point toward applications of such counter-ion-engineered zwitterionic materials in organic photoconductors, light-harvesting sensors, and interface layers for OLEDs and solar cells.

Norkov S.V. , Makarov S.G. , Travkin V.V. , Baranov E.V. , Fukin G.K. , Romanenko G.V. , Kuropatov V.A.
Stacking for success: Controlling molecular order in a new zwitterionic system for organic electronics
Journal of Molecular Structure. 2026. V.1372. 146637 :1-13. DOI: 10.1016/j.molstruc.2026.146637 WOS Scopus OpenAlex

Submitted:	Apr 2, 2026
Accepted:	May 22, 2026
Published online:	May 23, 2026
Published print:	Oct 15, 2026

≡ Web of science:	WOS:001785543200001
≡ Scopus:	2-s2.0-105040665995
≡ OpenAlex:	W7162216189