title: Monolayers as models for supported catalysts: zirconium phosphonate films containing manganese(III) porphyrins.
abstract: Organized monolayer films of a manganese tetraphenylporphyrin have been prepared and used as supported oxidation catalysts. Manganese 5,10,15,20-tetrakis(tetrafluorophenyl-4'-octadecyloxyphosphonic acid) porphyrin (1) has been immobilized as a monolayer film by a combination of Langmuir-Blodgett (LB) and self-assembled monolayer techniques that use zirconium phosphonate linkages to bind the molecule to the surface. Analysis by FTIR, XPS, UV-vis and polarized optical spectroscopy show that the films consist of noninteracting molecules effectively anchored and oriented nearly parallel to the surface. The monolayer films are stable to the solvent and temperature conditions needed to explore organic oxidations. The activity of films of 1 toward the epoxidation of cyclooctene using iodosylbenzene as the oxidant was compared to that of Manganese 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin (2) and 1 under equivalent homogeneous conditions. The immobilized porphyrin 1 shows an enhanced activity relative to either homogeneous reaction. The main difference between 1 and 2 is the four alkyl phosphonate arms in 1 designed to incorporate the porphyrin within the films. The increased activity of immobilized 1 is a combination of the porphyrin structure, which prohibits the formation of mu-oxo dimers even in solution, and a change in conformation when anchored to the surface. The study demonstrates that careful monolayer studies can provide useful models for the design and study of supported molecular catalyst systems.
authors.affiliation: Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, USA.
authors.forename: Isa O
authors.initials: IO
authors.lastname: Benítez
authors.forename: Bruno
authors.initials: B
authors.lastname: Bujoli
authors.forename: Laurent J
authors.initials: LJ
authors.lastname: Camus
authors.forename: Christine M
authors.initials: CM
authors.lastname: Lee
authors.forename: Fabrice
authors.initials: F
authors.lastname: Odobel
authors.forename: Daniel R
authors.initials: DR
authors.lastname: Talham