期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 24, 期 2, 页码 982-994出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1cp04321h
关键词
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资金
- DST SERB [ECR/2018/000923]
- Indian Institute of Technology Kharagpur [IIT/SRIC/CY/ENE/2018-19/194]
- French-Japan LIA (International Associate laboratory)
- ANR project Mol-CoSM [ANR-20-CE07-0028-02]
- University of Versailles
- University of Paris-Saclay-UPSAY
- CNRS (Centre National de la Recherche Scientifique)
- Swiss National Science Foundation [P400P2_191108/1]
- Indian Institute of Technology Kharagpur
- Romanian Ministry of Education and Research grant, CNCSUEFISCDI, PNCDI III [PN-III-P4-ID-PCE-2020-1946]
- Swiss National Science Foundation (SNF) [P400P2_191108] Funding Source: Swiss National Science Foundation (SNF)
This study investigates the behavior of the spin crossover compound [Fe(ptz)(6)](BF4)(2) in the host lattice of [Ru(ptz)(6)](BF4)(2), revealing a decoupling between crystallographic phase transitions and thermal spin transitions. Dilution with Ru reduces the cooperative character of the transition and results in observed hysteretic thermal transitions with slight domain formation. The transition temperature is slightly dependent on crystal properties, emphasizing the importance of Ru spatial distribution in addition to crystal shape and size.
The thermal spin transition and the photo-induced high-spin -> low-spin relaxation of the prototypical [Fe(ptz)(6)](BF4)(2) spin-crossover compound (ptz = 1-propyltetrazole) diluted in the isostructural ruthenium host lattice [Ru(ptz)(6)](BF4)(2), which stabilizes the Fe(ii) low-spin state, have been investigated. We demonstrate the presence of a crystallographic phase transition around 145 K (i.e. from the high-temperature ordered high-spin phase to a low-temperature disordered low-spin phase) upon slow cooling from room temperature. This crystallographic phase transition is decoupled from the thermal spin transition. A supercooled ordered low-spin phase is observed as in the pure Fe(ii) analogue upon fast cooling. A similar order-disorder phase transition is also observed for pure [Ru(ptz)(6)](BF4)(2) but at relatively higher temperature (i.e. at around 150 K) without involving any spin transition. For Ru-diluted [Fe(ptz)(6)](2+), the crystallographic phase transition as well as strong cooperative effects involving various degrees of elastic frustration are at the origin of stepped sigmoidal high-spin -> low-spin relaxation curves, which are modelled in the framework of a classical mean field model, considering both the tunnelling and thermally activated regimes. Optical microscopy studies performed on two different single crystals showed the existence of hysteretic thermal transitions with slight domain formation, hardly visible in the static crystal images. This behavior is attributed to the double effect upon Ru dilution, which decreases the cooperative character of the transition and simultaneously reduces the optical contrast between the LS and HS states. Moreover, the transition temperature revealed to be slightly crystal dependent, highlighting the crucial role of the spatial distribution of Ru from one crystal to another, in addition to the well-known effects of crystal shape and size.
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