Commutation thermo- et photo-induite de solides moléculaires a transition de spin : du monocristal aux nano-objets

Abstract : This work is devoted to synthesis of spin-crossover compounds and to the study of their thermo- or photo-induced switching. Photo-induced spin-crossover, either by the Light-Induced Excited Spin State Trapping (LIESST) or the Ligand Driven Light-Induced Spin Change (LD-LISC)) effects, has been studied in the solid state. The synthesis of spin-crossover nanoparticles built with compounds of molecular nature and the study of their switching properties has then been examined. The synthesis of optimized materials for the study of the photo-switching mechanism (LIESST effect) at ultrafast timescales has been developed and the first time-resolved measurements are presented. The study of the LD-LISC effect on the FeII(stpy)4(NCSe)2 (stpy = 4-styrylpyridine, photo-isomerizable ligand) complexes has also been performed, either bydispersing the compound in a polymeric matrix, or on the crystalline state. Different photo-induced behaviours have been evidenced, depending on the compound environment. On thecrystalline state, a unidirectional reactivity of the stpy ligand through an original mechanism following the excitation in the MLCT excited states has been evidenced. The synthesis of spin-crossover nanoparticles with compounds of molecular nature has then been performed with two different methods. First, the sol-gel process has been used to obtain well dispersed nanoparticles in a silica thin film. This approach allows the synthesis of size-controlled particles trapped on solids of good optical quality, in which a thermo- and photo-induced spin crossover has been observed with the [FeII(mepy)3tren](PF6)2 compound. Another synthetic method, based on the precipitation in an anti-solvent, has been successfully applied to various spin-crossover complexes. With the [FeIII(3-OMeSalEen)2]PF6 compound, size-controlled particles have been prepared and, interestingly, the size reduction effect on the cooperative processes appears to be limited. Finally, the study of FeII(phen)2(NCS)2 microcrystals has evidenced that the interaction between the polymer and the particles can affect their thermo- and photo-induced spin-crossover processes.
Document type :
Theses
Other. Université Paris Sud - Paris XI, 2011. French. <NNT : 2011PA112012>


https://tel.archives-ouvertes.fr/tel-00665234
Contributor : ABES STAR <>
Submitted on : Wednesday, February 1, 2012 - 2:37:16 PM
Last modification on : Thursday, February 2, 2012 - 1:08:38 PM

File

VD2_TISSOT_ANTOINE_28012011.pd...
fileSource_public_star

Identifiers

  • HAL Id : tel-00665234, version 1

Collections

Citation

Antoine Tissot. Commutation thermo- et photo-induite de solides moléculaires a transition de spin : du monocristal aux nano-objets. Other. Université Paris Sud - Paris XI, 2011. French. <NNT : 2011PA112012>. <tel-00665234>

Export

Share

Metrics

Consultation de
la notice

218

Téléchargement du document

99