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The First Photochemical In Situ Production of Ti‐Based Nanoparticles: A S H 2 Strategy Using Bis(cyclopentadienyl)titanium Dichloride (Cp 2 TiCl 2 )
Author(s) -
Versace DavyLouis,
Fouassier JeanPierre,
Lalevée Jacques
Publication year - 2014
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201300924
Subject(s) - photochemistry , cyclopentadienyl complex , homolysis , radical , titanium , chemistry , reactivity (psychology) , nanoparticle , electron paramagnetic resonance , photodissociation , materials science , catalysis , organic chemistry , nanotechnology , nuclear magnetic resonance , medicine , physics , pathology , alternative medicine
Bis(cyclopentadienyl)titanium dichloride (Cp 2 TiCl 2 ) is a high performance additive under UV light activation for both i) radical photopolymerization reactions (when added to a Type I photoinitiator such as 2,2‐dimethoxy‐2‐phenylacetophenone, the oxygen inhibition is reduced) and ii) a concomitant in situ photoinduced and oxygen mediated formation of Ti‐based nanoparticles (diameters ranging from 45 to 220 nm). The photochemical properties of Cp 2 TiCl 2 are investigated by steady state photolysis and electron spin resonance, and its photoinitiation ability checked. The nanoparticles (NPs) are well characterized by transmission electron microscopy. The high reactivity of Cp 2 TiCl 2 under air is ascribed to a bimolecular homolytic substitution (the S H 2 process is clearly demonstrated by density functional theory calculations and ESR experiments), which converts the peroxyls into new efficient initiating radicals. The photochemical in situ incorporation of Ti NPs has never previously been reported. The synthesis of metal nanoparticles by a S H 2 approach instead of the reduction of a metal salt appears to be a promising original method.