Engineering optical anisotropy in paramagnetic organic crystals: Dichroism of nitronyl nitroxide radicals

Engineering optical anisotropy in paramagnetic organic crystals: Dichroism of nitronyl nitroxide radicals Научная публикация

Журнал

Chinese Journal of Structural Chemistry
ISSN: 2949-768X

Вых. Данные

Год: 2025, Том: 44, Номер: 9, Номер статьи : 100653, Страниц : 8 DOI: 10.1016/j.cjsc.2025.100653

Авторы

Shurikov Matvey K. ¹ , Kolesnikova Yuliana A. ¹ , Votkina Darya E. ¹ , Abramov Pavel A. ^1,2 , Sukhikh Taisiya S. ² , Romanenko Galina V. ³ , Veber Sergey L. ³ , Gorbunov Dmitry E. ⁴ , Gritsan Nina P. ⁴ , Resnati Giuseppe ⁵ , Tretyakov Evgeny V. ⁶ , Kukushkin Vadim Yu. ⁷ , Postnikov Pavel S. ¹ , Petunin Pavel V. ¹

Организации

1	Research School of Chemistry & Applied Biomedical Sciences, Tomsk Polytechnic University, Lenin Av. 30, Tomsk, 634050, Russian Federation
2	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Lavrentieva Av. 3, Novosibirsk, 630090, Russian Federation
3	International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Institutskaya Str. 3a, Novosibirsk, 630090, Russian Federation
4	V.V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Institutskaya Str. 3, Novosibirsk, 630090, Russian Federation
5	NFMLab, Department of Chemistry, Materials and Chemical Engineering “Giulio Natta”, Politecnico di Milano, via Mancinelli 7, Milano I, 20131, Italy
6	N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Av. 47, Moscow, 119991, Russian Federation
7	Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg, 199034, Russian Federation

Six aryl- and pyridine-substituted nitronyl-nitroxide radicals were synthesized and characterized to investigate their optical anisotropic properties. Single-crystal X-ray diffraction analysis revealed molecular packing organized by either halogen and hydrogen bonding or hydrogen bonding alone. Single-crystal electronic absorption spectra in the visible region of three studied radicals exhibit pronounced linear dichroism, while single crystals of other radicals do not demonstrate this property. Time-dependent DFT and ab initio calculations were employed to determine the transition dipole moment (TDM) vectors corresponding to the long-wavelength absorption bands. For all radicals, these vectors are found to be practically parallel to the O⋯O direction of the nitronyl-nitroxide chromophore. Correlation between the dichroic properties and crystal structure was established through comprehensive analysis of TDM vector orientations relative to the crystal surface. The strongest dichroic effect was observed in crystals where all projections of the TDM vectors onto the illuminated face are parallel to each other, while weaker or absent effects correspond to non-parallel arrangements. This study constitutes the first systematic investigation of linear dichroism in paramagnetic organic crystals, thereby establishing new avenues for developing multifunctional materials that respond to both optical and magnetic stimuli.

Shurikov M.K. , Kolesnikova Y.A. , Votkina D.E. , Abramov P.A. , Sukhikh T.S. , Romanenko G.V. , Veber S.L. , Gorbunov D.E. , Gritsan N.P. , Resnati G. , Tretyakov E.V. , Kukushkin V.Y. , Postnikov P.S. , Petunin P.V.
Engineering optical anisotropy in paramagnetic organic crystals: Dichroism of nitronyl nitroxide radicals
Chinese Journal of Structural Chemistry. 2025. V.44. N9. 100653 :1-8. DOI: 10.1016/j.cjsc.2025.100653

Опубликована в печати:

1 сент. 2025 г.

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