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Keywords = soft X-ray induced excited spin state trapping

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12 pages, 4656 KiB  
Article
Thin Films of Nanocrystalline Fe(pz)[Pt(CN)4] Deposited by Resonant Matrix-Assisted Pulsed Laser Evaporation
by Dominik Maskowicz, Rafał Jendrzejewski, Wioletta Kopeć, Maria Gazda, Jakub Karczewski, Paweł Niedziałkowski, Armin Kleibert, Carlos A. F. Vaz, Yann Garcia and Mirosław Sawczak
Materials 2021, 14(23), 7135; https://doi.org/10.3390/ma14237135 - 24 Nov 2021
Cited by 7 | Viewed by 2242
Abstract
Prior studies of the thin film deposition of the metal-organic compound of Fe(pz)Pt[CN]4 (pz = pyrazine) using the matrix-assisted pulsed laser evaporation (MAPLE) method, provided evidence for laser-induced decomposition of the molecular structure resulting in a significant downshift of the spin transition [...] Read more.
Prior studies of the thin film deposition of the metal-organic compound of Fe(pz)Pt[CN]4 (pz = pyrazine) using the matrix-assisted pulsed laser evaporation (MAPLE) method, provided evidence for laser-induced decomposition of the molecular structure resulting in a significant downshift of the spin transition temperature. In this work we report new results obtained with a tunable pulsed laser, adjusted to water resonance absorption band with a maximum at 3080 nm, instead of 1064 nm laser, to overcome limitations related to laser–target interactions. Using this approach, we obtain uniform and functional thin films of Fe(pz)Pt[CN]4 nanoparticles with an average thickness of 135 nm on Si and/or glass substrates. X-ray diffraction measurements show the crystalline structure of the film identical to that of the reference material. The temperature-dependent Raman spectroscopy indicates the spin transition in the temperature range of 275 to 290 K with 15 ± 3 K hysteresis. This result is confirmed by UV-Vis spectroscopy revealing an absorption band shift from 492 to 550 nm related to metal-to-ligand-charge-transfer (MLCT) for high and low spin states, respectively. Spin crossover is also observed with X-ray absorption spectroscopy, but due to soft X-ray-induced excited spin state trapping (SOXIESST) the transition is not complete and shifted towards lower temperatures. Full article
(This article belongs to the Special Issue Preparation and Properties of Thin Films)
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9 pages, 2926 KiB  
Article
Soft X-ray Absorption Spectroscopy Study of Spin Crossover Fe-Compounds: Persistent High Spin Configurations under Soft X-ray Irradiation
by Ahmed Yousef Mohamed, Minji Lee, Kosuke Kitase, Takafumi Kitazawa, Jae-Young Kim and Deok-Yong Cho
Crystals 2018, 8(11), 433; https://doi.org/10.3390/cryst8110433 - 19 Nov 2018
Cited by 12 | Viewed by 6196
Abstract
Metal-organic complex exhibiting spin crossover (SCO) behavior has drawn attention for its functionality as a nanoscale spin switch. The spin states in the metal ions can be tuned by external stimuli such as temperature or light. This article demonstrates a soft X-ray–induced excited [...] Read more.
Metal-organic complex exhibiting spin crossover (SCO) behavior has drawn attention for its functionality as a nanoscale spin switch. The spin states in the metal ions can be tuned by external stimuli such as temperature or light. This article demonstrates a soft X-ray–induced excited spin state trapping (SOXEISST) effect in Hofmann-like SCO coordination polymers of FeII(4-methylpyrimidine)2[Au(CN)2]2 and FeII(pyridine)2[Ni(CN)4]. A soft X-ray absorption spectroscopy (XAS) study on these polymers showed that the high spin configuration (HS; S = 2) was prevalent in Fe2+ ions during the measurement even at temperatures much lower than the critical temperatures (>170 K), manifesting HS trapping due to the X-ray irradiation. This is in strong contrast to the normal SCO behavior observed in FeII(1,10-phenanthroline)2(NCS)2, implying that the structure of the ligand chains in the polymers with relatively loose Fe-N coordination might allow a structural adaptation to stabilize the metastable HS state under the soft X-ray irradiation. Full article
(This article belongs to the Special Issue Synthesis and Applications of New Spin Crossover Compounds)
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