A comparison is reported for thermally and photo-induced high-spin phases of [Fe(2-pic)3]Cl2.EtOH (2-pic: 2-picolylamine) using the nuclear resonant inelastic scattering (NRIS) technique.
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http://dx.doi.org/10.1039/b409025j | DOI Listing |
Chem Sci
June 2023
State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, Dalian University of Technology 2 Linggong Road Dalian 116024 China
Manipulating fluorescence by photo-switched spin-state conversions is an attractive prospect for applications in smart magneto-optical materials and devices. The challenge is how to modulate the energy transfer paths of the singlet excited state by light-induced spin-state conversions. In this work, a spin crossover (SCO) Fe-based fluorophore was embedded into a metal-organic framework (MOF) to tune the energy transfer paths.
View Article and Find Full Text PDFInt J Mol Sci
November 2022
GEMaC, CNRS, Université de Versailles Saint Quentin en Yvelines, 45 Avenue des Etats Unis, CEDEX, 78035 Versailles, France.
Spin-crossover solids have been studied for many years for their promising applications as optical switches and reversible high-density memories for information storage. This study reports the effect of random metal dilution on the thermal and structural properties of a spin-crossover single crystal. The analysis is performed on a 2D rectangular lattice using an electro-elastic model.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2022
Université Paris-Saclay, UVSQ, CNRS, GEMAC, 45 Avenue des Etats Unis 78035, Versailles, France.
The thermal spin transition and the photo-induced high-spin → low-spin relaxation of the prototypical [Fe(ptz)](BF) spin-crossover compound (ptz = 1-propyltetrazole) diluted in the isostructural ruthenium host lattice [Ru(ptz)](BF), which stabilizes the Fe(II) low-spin state, have been investigated. We demonstrate the presence of a crystallographic phase transition around 145 K ( 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.
View Article and Find Full Text PDFInorg Chem
September 2021
Department of Chemistry, Southern University of Science and Technology (SUSTech), Shenzhen 518055, China.
A family of molecular capsules, {[(Tp*)Fe(CN)Co(bpybpy)][X]}·sol (, X = ClO, sol = 6DMF; , X = PF, sol = 6DMF; , X = OTf, sol = 6DMF; , X = BPh, sol = 2DMF; Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate; bpy = 2,2'-bipyridine), were prepared via the Schiff-base condensation of the aldehyde-substituted bpy (bpy) and 1,7-diaminoheptane (HN(CH)NH). All the complexes contain the same cyanide-bridged cationic square cores ([FeCo]), which are encapsuled by the flexible alkyl chains. Variable-temperature single-crystal X-ray diffraction, FT-IR spectra, and magnetic studies reveal the abrupt and complete, thermo- and photo-induced electron-transfer-coupled spin transition for -, while the pure high-spin phase for .
View Article and Find Full Text PDFIn condensed phase chemistry, the solvent can have a significant impact on everything from yield to product distribution to mechanism. With regard to photo-induced processes, solvent effects have been well-documented for charge-transfer states wherein the redistribution of charge subsequent to light absorption couples intramolecular dynamics to the local environment of the chromophore. Ligand-field excited states are expected to be largely insensitive to such perturbations given that their electronic rearrangements are localized on the metal center and are therefore insulated from so-called outer-sphere effects by the ligands themselves.
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