Supramolecular Organization in Organic–Inorganic Heterogeneous Hybrid Catalysts Formed from Polyoxometalate and Poly(ampholyte) Polymer

• DOI: 10.1021/la400055t
• Publication Date: 2013-03-12T22:36:01Z
• Authors: Gijo Raj; Colas Swalus; Alain Guillet; Michel Devillers; Bernard Nysten; Eric M. Gaigneaux
• Keywords: Polyoxometalate; Hybrid material; Supramolecular Polymers; Supramolecular assembly

Hybridization of polyoxometalates (POMs) via the formation an organic–inorganic association constitutes a new route to develop heterogeneous POM catalyst with tunable functionality imparted through supramolecular assembly. Herein, we report on strategies obtain well-defined architectures hybrid formed by hydrophobically substituted polyampholyte copolymer (poly N, N-diallyl-N-hexylamine-alt-maleic acid) and phosphotungstic acid (H3PW12O40) POMs. The self-assembling property initial matrix is modulated controlling pH hybridization solution. When deposited mica surface, isolated, long extended polymer chains are under basic conditions (pH 7.9), while globular or coiled structures acidic 2). assembly POM-polymer found be directed type quantities charges present copolymer, which themselves depend conditions. hypothesis that Keggin [PW12O40]3– anions, have size ∼1 nm, electrostatically bind positive charge sites backbone. material stabilized at 5.3 consists POM-decorated chains. Statistical analysis distances between pairs entities show narrow density distributions, suggesting attached high level order. Conversely, 2), shows core–shell structure. reported here, tune materials, highly valuable for design more rational utilization catalysts in several chemical transformations.