Synthesis and Characterization of Face-to-Face Arylsulfanyl and Phenoxyl Radicals Embedded in Mesoporous Silicas - Archive ouverte HAL Access content directly
Journal Articles Journal of Physical Chemistry C Year : 2023

Synthesis and Characterization of Face-to-Face Arylsulfanyl and Phenoxyl Radicals Embedded in Mesoporous Silicas

Pierre Nabokoff
  • Function : Author
Guillaume Brulay
  • Function : Author
Cyrielle Dol
  • Function : Author
Emily Bloch
  • Function : Author
Fabio Ziarelli
  • Function : Author
Eric Besson
  • Function : Author
Stéphane Gastaldi

Abstract

Recent applications of bi-, oligo-or polyradicals to spin sciences have generated considerable interest in the design of new bi/oligoradical organic molecules. Nevertheless, studies of physicochemical properties open shell systems are generally based on stable homonuclear organic radicals, which represent only a small portion of the existing radicals. In this context, diazene precursors of heteroatomic radicals were incorporated into the 2 SBA-15 silica framework. Photolysis at 360 nm of the diazene moiety resulted in the formation of two face-to-face oxygen-and sulfur-centered radicals. These systems were characterized by X-, Q-and W-band EPR spectroscopy by comparing them to silicas functionalized with either face-to-face sulfur-centered radicals or face-to-face oxygencentered radicals. These EPR studies allowed measuring their half-life as well as their relaxation times (T1 and T2). The properties of silicas functionalized with sulfur-and oxygen-centered radicals fall between those measured for the two reference systems functionalized with only sulfur-or oxygen-centered radicals. These nanostructured silicas functionalized by two radicals of different nature are new potential candidates as polarizing agent for DNP NMR.
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Dates and versions

hal-04114864 , version 1 (02-06-2023)

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Pierre Nabokoff, Guillaume Brulay, Cyrielle Dol, Guillaume Gerbaud, Bruno Guigliarelli, et al.. Synthesis and Characterization of Face-to-Face Arylsulfanyl and Phenoxyl Radicals Embedded in Mesoporous Silicas. Journal of Physical Chemistry C, 2023, 127 (20), pp.9699-9706. ⟨10.1021/acs.jpcc.3c01550⟩. ⟨hal-04114864⟩
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