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Phenylethynylstyrene−Cobalt Carbonyl Block Copolymer Composites

“…Complexation of Co 2 (CO) 6 groups to the alkyne-functional polymer was further confirmed by IR spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). Comparison of IR spectra of PS-PPES to spectra of PS-PPES[Co 2 (CO) 6 ] shows disappearance of the PS-PPES ν C ≡ C band (2225 cm -1 ) after treatment with Co 2 (CO) 8 and appearance of strong bands at 2015, 2048, and 2083 cm -1 , which correspond to terminal CO groups in small molecule diarylacetylene−Co 2 (CO) 6 adducts, and a band at 1600 cm -1 , due to the Co-coordinated alkyne (Figure a). ,, These PS-PPES[Co 2 (CO) 6 ] adducts appear to be quite stable to thermolysis in solution. For example, even after 17 h in refluxing toluene at a concentration of 30 mg/mL, the intensity of the CO bands in the IR spectrum of PS 173 PPES 67 [Co 2 (CO) 6 ] 61 does not appear to be diminished (see Supporting Information), and elemental analysis suggests the presence of three CO ligands per Co atom (Table , entry 4).…”

“…One potential application of such composite systems arises from the increasing storage density requirements in microelectronic devices and the resulting drive for development of magnetic nanomaterials with addressable elements on the nanometer scale. Discrete nanometer-scale magnetic regions, such as those found in materials containing magnetic metallic nanoparticles, appear to be one promising choice in information storage, where magnetic and optical storage components as small as tens of nanometers will be needed in the future. , In such applications, where magnetic or redox properties are important, cobalt-containing systems represent a major class of useful materials . Cobalt nanomaterials are typically prepared by reduction of Co(II) salts or thermolysis of Co 2 (CO) 8 in the presence of a range of stabilizing molecules, which prevent aggregation into larger agglomerates. , …”

“…Several reports documenting the preparation of homopolymers with alkyne-functional backbones through condensation or ring-opening polymerization and their subsequent reaction with cobalt ,, or platinum have appeared. Here we report the incorporation of cobalt carbonyl groups within the alkyne functional blocks of polystyrene- block -poly(4-(phenylethynyl)styrene) copolymers and the resulting phase separation.…”

Highly Metallized Polymers: Synthesis, Characterization, and Lithographic Patterning of Polyferrocenylsilanes with Pendant Cobalt, Molybdenum, and Nickel Cluster Substituents

“…Through radical copolymerization of cluster-containing monomers or macromolecular substitution of a copolymer with a metal cluster, Pomogailo and co-workers have synthesized a variety of cluster-containing copolymers with molybdenum, osmium, or rhodium clusters . Allen and Bahadur have reported complexation of phenylethynyl substituents with [Co 2 (CO) 8 ] in a styrene copolymer containing phenylacetylide-substituted pendant cyclophosphazenes . Several examples of metallopolymers with metal clusters in the backbone have also been reported.…”

N-(Ferrocenylmethyl)-N-methylaminocyclotriphosphazenes

“…To provide materials to continue our studies of hybrid organic−inorganic polymers with redox active cyclophosphazenes, we investigated the synthesis of mixed substituent cyclophosphazenes containing both 2 and an olefin-containing substituent. To accomplish this, (methacyloylbutenedioxy)pentachlorocyclotriphosphazene, 8 , was allowed to react with 2 equiv of 2 .…”