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926979.pdf (3.75 MB)

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2026-02-26

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cc-by (c) Buravlev, Alexander A. et al., 2026
Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/229506

Stable 1,3,2-Benzodithiazolyl Radicals: Modification ofReactivity, Crystal Packing, and Solid State MagneticProperties by Fluorination

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https://doi.org/10.1002/open.202500561

Resum

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-tetra-fluoro, 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.

Matèries

Propietats magnètiques, Estructura molecular, Ciència dels materials

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Magnetic properties, Molecular structure, Materials science

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Articles publicats en revistes (Ciència dels Materials i Química Física)
Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB))

Citació

BURAVLEV, Alexander A., et al. Stable 1,3,2-Benzodithiazolyl Radicals: Modification ofReactivity, Crystal Packing, and Solid State MagneticProperties by Fluorination. ChemistryOpen. 2026. Vol. 15, num. 3, pags. e202500561. ISSN 2191-1363. [consulted: 19 of August of 2026]. Available at: https://hdl.handle.net/2445/229506

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