1 research outputs found
Immobilization of Volatile and Corrosive Iodine Monochloride (ICl) and I<sub>2</sub> Reagents in a Stable Metal–Organic Framework
The
major discovery here is a robust and water-stable metal–organic
framework (MOF) material capable of reversible binding of the volatile
and reactive molecules of ICl and I<sub>2</sub>. The immobilization
of I<sub>2</sub> and ICl, as well as their controllable release thus
achieved, is to facilitate the wide-ranging applications of these
volatile species as catalysts and reagents in chemical and industrial
processes. The framework material TMBP·CuI (hereafter TCuI) can
be conveniently prepared in quantitative yields by heating CuI and
the organic linker TMBP (3,3′,5,5′-tetramethyl-4,4′-bipyrazol)
in acetonitrile. The microporous three-dimensional net of TCuI features
CuI chains that contribute to efficient and reversible binding of
ICl and I<sub>2</sub> molecules, to result in the stoichiometrically
well-defined adducts of TCuI·ICl and TCuI·I<sub>2</sub>,
respectively. Moreover, the confinement of a volatile compound like
ICl within the MOF medium provides unique opportunities to enhance
its reactivity and selectivity as a chemical reagent, as is exemplified
by the iodination reactions examined herein. With this exemplary study,
we intend to stimulate interest in further exploring MOFs and other
porous media (e.g., porous polymers) for entrapping ICl and other
volatile reagents (e.g., Br<sub>2</sub>, SCl<sub>2</sub>, S<sub>2</sub>Cl<sub>2</sub>, and SOCl<sub>2</sub>) and for potentially novel reactivity
associated with the porous medium