Hysteretic Room‐Temperature Magnetic Bistability of the Crystalline 4,7‐Difluoro‐1,3,2‐Benzodithiazolyl Radical

Hysteretic Room‐Temperature Magnetic Bistability of the Crystalline 4,7‐Difluoro‐1,3,2‐Benzodithiazolyl Radical Full article

Journal

ChemPlusChem
ISSN: 2192-6506

Output data

Year: 2024, Article number : e202300736, Pages count : 9 DOI: 10.1002/cplu.202300736

Tags

1,3,2-benzodithiazolyls; fluoroorganics; magnetic bistability; magnetic hysteresis; synthesis

Authors

Makarov Alexander Yurievich ¹ , Buravlev Alexander A. ^1,5 , Romanenko Galina V. ² , Bogomyakov Artem S. ² , Zakharov Boris A. ^3,5 , Morozov Vitaly A. ² , Sukhikh Alexander S. ^4,6 , Shundrina Inna K. ¹ , Shundrin Leonid A. ¹ , Irtegova Irina G. ¹ , Cherepanova Svetlana V. ³ , Bagryanskaya Irina Yu. ¹ , Nikulshin Pavel V. ^1,7 , Zibarev Andrey V. ¹

Affiliations

1	Vorozhtsov Institute of Organic Chemistry Siberian Branch, Russian Academy of Sciences 630090 Novosibirsk (Russia)
2	International Tomography Center Siberian Branch, Russian Academy of Sciences 630090 Novosibirsk (Russia)
3	Boreskov Institute of Catalysis Siberian Branch, Russian Academy of Sciences 630090 Novosibirsk (Russia)
4	Nikolaev Institute of Inorganic Chemistry Siberian Branch, Russian Academy of Sciences 630090 Novosibirsk (Russia)
5	Department of Natural Sciences National Research University – Novosibirsk State University 630090 Novosibirsk (Russia)
6	Department of Physics National Research University – Novosibirsk State University 630090 Novosibirsk (Russia)
7	Topchiev Institute of Petrochemical Synthesis Russian Academy of Sciences 119991 Moscow (Russia)

The title radical R·, synthesized by reduction of the corresponding cation R+, is thermally stable up to ~380 K in the crystalline state under anaerobic conditions. With SQUID magnetometry, single-crystal and powder XRD, solid-state EPR and TG-DSC, reversible spin-Peierls transition between diamagnetic and paramagnetic states featuring ~10 K hysteretic loop is observed for R· in the temperature range ~ 310-325 K; ΔH = ~2.03 kJ mol–1 and ΔS = ~6.23 J mol–1 K–1. The transition is accompanied by mechanical movement of the crystals, i.e., by thermosalient behavior. The low-temperature diamagnetic P–1 polymorph of R· consists of R·2 π-dimers arranged in (…R·2…)n π-stacks; whereas the high-temperature paramagnetic P21/c polymorph, of uniform (…R·…)n π-stacks. With the XRD geometries, CASSCF and broken-symmetry DFT jointly suggest strong antiferromagnetic (AF) interactions within R·2 and weak between R·2 for the (…R·2…)n stacks; and moderate AF interactions between R· for the (…R·…)n stacks. The fully hydrocarbon archetype of R· does not reveal the aforementioned properties. Thus, the fluorinated 1,3,2-benzodithiazolyls pave a new pathway in the design and synthesis of metal-less magnetically-bistable materials.

Makarov A.Y. , Buravlev A.A. , Romanenko G.V. , Bogomyakov A.S. , Zakharov B.A. , Morozov V.A. , Sukhikh A.S. , Shundrina I.K. , Shundrin L.A. , Irtegova I.G. , Cherepanova S.V. , Bagryanskaya I.Y. , Nikulshin P.V. , Zibarev A.V.
Hysteretic Room‐Temperature Magnetic Bistability of the Crystalline 4,7‐Difluoro‐1,3,2‐Benzodithiazolyl Radical
ChemPlusChem. 2024. e202300736 :1-9. DOI: 10.1002/cplu.202300736 WOS Scopus

Submitted:	Dec 13, 2023
Accepted:	Feb 8, 2024
Published online:	Feb 8, 2024

Web of science	WOS:001176598600001
Scopus	2-s2.0-85185942081
OpenAlex	W4391687881