Spin transition and symmetry-breaking in new mononuclear FeII tren-complexes with up to 38 K hysteresis around room temperature
| Autor: | Francisco Javier Valverde-Muñoz, Maksym Seredyuk, Igor O. Fritsky, José Antonio A Real Cabezos, Vladimir M. Amirkhanov, Kateryna O. Znovjyak, M. Carmen Muñoz |
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| Rok vydání: | 2022 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry Frontiers. 9:537-546 |
| ISSN: | 2052-1553 |
| DOI: | 10.1039/d1qi00941a |
| Popis: | [EN] The structurally simple complex {Fe-II[tren(6F-py)(3)]}(BF4)(2) [tren(6F-py)(3) = tris(3-aza-4-(6-fluoro-2-pyridyl)-3-butenyl)amine] undergoes an abrupt spin transition (ST) with the critical temperature T down arrow(1/2) = 243 K on cooling and T up arrow(1/2) = 281 K on heating, with a 38 K wide hysteresis, while the ClO4- congener shows ST spanning the room temperature region at T down arrow(1/2) = 267 K and T up arrow(1/2) = 295 K with a 28 K wide hysteresis. Calorimetric data confirm the occurrence of a highly energetic ST process, while multi-temperature single crystal X-ray structural studies identify a concerted symmetry-breaking P2(1)/n P2(1)/c as the origin of the rare strong cooperativity and the large hysteresis loop. The analysis of the experimental data discloses two distinct interdependent events, namely, the combination of a gradual ST and an induced crystallographic phase transition, which endows the material with strong bistability and makes it an excellent platform for investigating new generations of ST based electronic and spintronic devices. This work was supported by grant PID2019-106147GB-I00 funded by MCIN/AEI/10.13039/501100011033, Unidad de Excelencia Maria de Maeztu (CEX2019-000919-M); the Generalitat Valenciana through PROMETEO/2016/147 and EU Framework FET-OPEN project COSMICS (grant agreement 766726), by the grant of the Ministry of Education and Science of Ukraine for perspective development of a scientific direction "Mathematical sciences and natural sciences" at Taras Shevchenko National University of Kyiv. We thank Prof. Dr Eric Collet for invaluable comments and suggestions. |
| Databáze: | OpenAIRE |
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