Stable 1,3,2-Benzodithiazolyl Radicals: Modification of Reactivity, Crystal Packing, and Solid State Magnetic Properties by Fluorination.

Stable 1,3,2-Benzodithiazolyl Radicals: Modification of Reactivity, Crystal Packing, and Solid State Magnetic Properties by Fluorination. Научная публикация

Журнал

ChemistryOpen
ISSN: 2191-1363

Вых. Данные

Год: 2026, Том: 15, Номер: 3, Номер статьи : e202500561, Страниц : 21 DOI: 10.1002/open.202500561

Авторы

Buravlev Alexander A ^1,2 , Makarov Alexander Yu ¹ , Ribas-Ariño Jordi ³ , Carvajal M Àngels ³ , Deumal Mercè ³ , Balmohammadi Yaser ⁴ , Grabowsky Simon ⁴ , Shundrina Inna K ¹ , Zakharov Boris A ^2,5 , Irtegova Irina G ¹ , Uvarov Mikhail N ⁶ , Bogomyakov Artem S ⁷ , Bagryanskaya Irina Yu ¹ , Shundrin Leonid A ¹ , Zibarev Andrey V ¹

Организации

1	Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia
2	Department of Natural Sciences, National Research University - Novosibirsk State University, Novosibirsk, Russia
3	Departament de Ciència de Materials i Química Física, and Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, Barcelona, Spain
4	Department of Chemistry, Biochemistry, and Pharmaceutical Sciences, University of Bern, Bern, Switzerland
5	Synchrotron Radiation Facility - Siberian Circular Source of Photons (SRF «SKIF»), Novosibirsk, Russia
6	Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia
7	International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia

Impact of fluorination on crystal and molecular structure, heteroatom reactivity, and solid-state magnetic properties of thermally-stable π-radicals is studied experimentally and computationally with 1,3,2-benzodithiazolyl 1· and its 4,7-difluoro, 4,5,6,7-tetrafluoro, and 4,7-difluoro-5,6-(hexafluoropropane-1,3-diyl) derivatives 2·-4·, respectively. Radicals 2·-4· are isolated by vacuum thermolysis of their unusual covalent 2:1 adducts with 7,7,8,8-tetracyanoquinodimethane. The impact of fluorination on reactivity is evidenced by transformation of 2·-4· and 2+-4+ into corresponding 2H-1-oxo-1,3,2-benzodithiazoles under the influence of air's or solvents’ moisture; back transformation into the cations under the action of protic acids; and formation of a paramagnetic molecular complex between 3· and naphthalene, whereas 1· and octafluoronaphthalene do not exhibit complexation. The crystal structures of 3· and 4· reveal a novel packing motif featuring radical pairs linked by four-center interactions that stack into offset π-columns, forming a unique zip-π-stack synthon that incorporates head-over-tail π-pairs of radicals. Despite the formation of π-pairs, polycrystalline 3· and 4· display a nonzero effective magnetic moment that rises with temperature above 200 K, although the values remain significantly lower than those of the high-temperature polymorphs of magnetically-bistable 1· and 2·. This behavior can be rationalized by different magnetic topologies and values of spin exchange between the radicals.

Buravlev A.A. , Makarov A.Y. , Ribas-Ariño J. , Carvajal M.À. , Deumal M. , Balmohammadi Y. , Grabowsky S. , Shundrina I.K. , Zakharov B.A. , Irtegova I.G. , Uvarov M.N. , Bogomyakov A.S. , Bagryanskaya I.Y. , Shundrin L.A. , Zibarev A.V.
Stable 1,3,2-Benzodithiazolyl Radicals: Modification of Reactivity, Crystal Packing, and Solid State Magnetic Properties by Fluorination.
ChemistryOpen. 2026. V.15. N3. e202500561 :1-21. DOI: 10.1002/open.202500561 Scopus OpenAlex

Поступила в редакцию:	22 окт. 2025 г.
Принята к публикации:	2 дек. 2025 г.
Опубликована online:	26 февр. 2026 г.
Опубликована в печати:	1 мар. 2026 г.

≡ Scopus:	2-s2.0-105031315450
≡ OpenAlex:	W7131621617