Metal Atom Routes to Metal-Based Clusters in Polymers

Past syntheses of polymer composites have largely evolved from chemical reduction or thermal decomposition of organometallic or inorganic precursor molecules in polymers, or plasma and thermal co-deposition of metal vapors and carbonaceous free radicals. Our approach involves the site-specific capture of metal atoms deposited in vacuum to give isolated, high energy mononuclear organometallic centers within a polymer film. These centers can be converted at ambient or sub-ambient temperatures (ie, below the polymer glass transition temperature) to, for example, metal oxide microclusters. We describe the results of our studies of a prototypical system involving chromium atoms and their conversion to corundum-type oxide microclusters in arene-functionalized polymer films. Thus Cr was deposited into 150 K liquid tetrahydrofuran solutions of polystyrene or poly(styrene-isoprene-styrene) triblock, spun in vacuo as thin films on the surface of a rotating glass cryostat. Evidence from epr spectrscopy shows that the resulting polymer-anchored (inter/intra-chain) bis(arene)Cr sandwich complex is locally mobile in the macroscopically rigid film at room temperature. The Cr atom is discharged from the rings by subsequent reaction with oxygen diffused into the film. Although α Cr2 O3 is a classic twosublevel antiferromagnet that is not epr active above 308 K, we observe an intense signal even at 77 K in these films. Cr2O3 microclusters are indicated, and these are confirmed by in situ measurements of the oxidation and aggregation process. The metal atom methodology has also been used to synthesize silver microsphere/polymer composites. With quadratic electrooptic phase modulation, these composites were found to show a third order susceptibility enhanced by coupling the dipolar surface plasmon mode of the particles with incident light.