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,
Volume: 89,
Number: 6,
Article number
: e202300736,
Pages count
: 9
DOI:
10.1002/cplu.202300736
|
| Tags |
1,3,2-benzodiathiazolyls · fluoroorganics · magnetic bistability · magnetic hysteresis · synthesis |
| Authors |
Makarov Alexander Yu.
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)
|
|
Funding (4)
|
1
|
Russian Science Foundation
|
23-13-00014 (123061600018-8)
|
|
2
|
Ministry of Science and Higher Education of the Russian Federation
|
FWUZ-2021-0005 (121031700313-8)
|
|
3
|
Ministry of Science and Higher Education of the Russian Federation
|
FWUE-2022-0004 (122040800264-3)(15326-03-13-660)
|
|
4
|
Ministry of Science and Higher Education of the Russian Federation
|
Приоритет 2030
|
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.