Monitoring of Fe(II) Spin Transition in Cu(II)-Doped Spin-Crossover Nanoparticles
Experimental protocols based on Electron Paramagnetic Resonance (EPR) and Raman spectroscopy are presented for the investigation of the Fe(II) spin transition in Cu(II)-doped 1-D spin-crossover (SCO) nanoparticles of the type [Fe<sub>1−x</sub>Cu<sub>x</sub>(NH<sub>2<...
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MDPI AG
2025-03-01
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| author | Alexander Charitos Vassilis Tangoulis John Parthenios Ondrej Malina Radim Mach Nikolaos Ioannidis Nikolia Lalioti |
| author_facet | Alexander Charitos Vassilis Tangoulis John Parthenios Ondrej Malina Radim Mach Nikolaos Ioannidis Nikolia Lalioti |
| author_sort | Alexander Charitos |
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| description | Experimental protocols based on Electron Paramagnetic Resonance (EPR) and Raman spectroscopy are presented for the investigation of the Fe(II) spin transition in Cu(II)-doped 1-D spin-crossover (SCO) nanoparticles of the type [Fe<sub>1−x</sub>Cu<sub>x</sub>(NH<sub>2</sub>trz)<sub>3</sub>]Br<sub>2</sub> where x = 0.03 and 0.06 and NH<sub>2</sub>trz = 4-amino-1, 2, 4-triazole. The resulting nanoparticles were characterized using Transmission Electron Microscopy (TEM), Infrared (IR) spectroscopy, and powder X-ray diffraction (p-XRD). Magnetic susceptibility measurements revealed a dependence on the scan rate, with critical temperatures and hysteresis widths varying accordingly. EPR spectroscopy provided insights into the doped nanoparticles’ structural changes and spin-state transitions. The Cu(II) dopants exhibited significant g-factor anisotropy and hyperfine structure, indicative of a distorted octahedral coordination. The EPR spectra indicated that the spin transition occurs in domains populated by ions of the same spin state. Cu(II) ions show different spectral characteristics depending on whether they are in high-spin or low-spin domains of Fe(II). Changes in Raman bands induced by laser power reveal structural and electronic rearrangements during the LS to HS transition. The findings provide insights into metal–ligand interactions and the molecular mechanisms underlying the SCO process. |
| format | Article |
| id | doaj-art-596f60260636495ab8a9a9bdf2b573e1 |
| institution | OA Journals |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-03-01 |
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| spelling | doaj-art-596f60260636495ab8a9a9bdf2b573e12025-08-20T01:48:48ZengMDPI AGMolecules1420-30492025-03-01306125810.3390/molecules30061258Monitoring of Fe(II) Spin Transition in Cu(II)-Doped Spin-Crossover NanoparticlesAlexander Charitos0Vassilis Tangoulis1John Parthenios2Ondrej Malina3Radim Mach4Nikolaos Ioannidis5Nikolia Lalioti6Laboratory of Inorganic Chemistry, Department of Chemistry, University of Patras, 26504 Patras, GreeceLaboratory of Inorganic Chemistry, Department of Chemistry, University of Patras, 26504 Patras, GreeceInstitute of Chemical Engineering Sciences (ICE-HT), Foundation for Research and Technology-Hellas (FORTH), 26504 Patras, GreeceRegional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute (CATRIN), Palacký University Olomouc, Šlechtitelů 27, 78371 Olomouc, Czech RepublicRegional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute (CATRIN), Palacký University Olomouc, Šlechtitelů 27, 78371 Olomouc, Czech RepublicInstitute of Nanoscience and Nanotechnology, NCSR “Demokritos”, 15310 Athens, GreeceLaboratory of Inorganic Chemistry, Department of Chemistry, University of Patras, 26504 Patras, GreeceExperimental protocols based on Electron Paramagnetic Resonance (EPR) and Raman spectroscopy are presented for the investigation of the Fe(II) spin transition in Cu(II)-doped 1-D spin-crossover (SCO) nanoparticles of the type [Fe<sub>1−x</sub>Cu<sub>x</sub>(NH<sub>2</sub>trz)<sub>3</sub>]Br<sub>2</sub> where x = 0.03 and 0.06 and NH<sub>2</sub>trz = 4-amino-1, 2, 4-triazole. The resulting nanoparticles were characterized using Transmission Electron Microscopy (TEM), Infrared (IR) spectroscopy, and powder X-ray diffraction (p-XRD). Magnetic susceptibility measurements revealed a dependence on the scan rate, with critical temperatures and hysteresis widths varying accordingly. EPR spectroscopy provided insights into the doped nanoparticles’ structural changes and spin-state transitions. The Cu(II) dopants exhibited significant g-factor anisotropy and hyperfine structure, indicative of a distorted octahedral coordination. The EPR spectra indicated that the spin transition occurs in domains populated by ions of the same spin state. Cu(II) ions show different spectral characteristics depending on whether they are in high-spin or low-spin domains of Fe(II). Changes in Raman bands induced by laser power reveal structural and electronic rearrangements during the LS to HS transition. The findings provide insights into metal–ligand interactions and the molecular mechanisms underlying the SCO process.https://www.mdpi.com/1420-3049/30/6/1258Fe-triazolespin crossoverEPRRamanthermal hysteresis |
| spellingShingle | Alexander Charitos Vassilis Tangoulis John Parthenios Ondrej Malina Radim Mach Nikolaos Ioannidis Nikolia Lalioti Monitoring of Fe(II) Spin Transition in Cu(II)-Doped Spin-Crossover Nanoparticles Molecules Fe-triazole spin crossover EPR Raman thermal hysteresis |
| title | Monitoring of Fe(II) Spin Transition in Cu(II)-Doped Spin-Crossover Nanoparticles |
| title_full | Monitoring of Fe(II) Spin Transition in Cu(II)-Doped Spin-Crossover Nanoparticles |
| title_fullStr | Monitoring of Fe(II) Spin Transition in Cu(II)-Doped Spin-Crossover Nanoparticles |
| title_full_unstemmed | Monitoring of Fe(II) Spin Transition in Cu(II)-Doped Spin-Crossover Nanoparticles |
| title_short | Monitoring of Fe(II) Spin Transition in Cu(II)-Doped Spin-Crossover Nanoparticles |
| title_sort | monitoring of fe ii spin transition in cu ii doped spin crossover nanoparticles |
| topic | Fe-triazole spin crossover EPR Raman thermal hysteresis |
| url | https://www.mdpi.com/1420-3049/30/6/1258 |
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