Incorporation of Polyoxometalates into Polymers to Create Linear Poly(polyoxometalate)s with Catalytic Function

Abstract

Organic polymers have been found widespread commercial applications due to their easy processing and attractive mechanical properties. Concurrently, inorganic polyoxometalates (POMs), a class of metal–oxygen anionic and nanosized clusters of early transition metals, have a wide range of attractive functions and are used in industrial catalysis. In this communication, we report a new approach to creating the first linear poly(polyoxometalate)s that combine the advantages of polymers and POM clusters. In the experiment, a POM-containing norbornene monomer was first synthesized by linking a Wells-Dawson-type POM with a norbornene derivative. The monomer was polymerized in the presence of a Grubbs catalyst under mild conditions with yields nearly 100% in a living and controllable manner. The resulting poly(polyoxometalate)s have controllable molecular weights and a well-defined hybrid structure of an organic polynorbornene backbone with large pendant groups of the nanosized POM clusters. Thus, they form good films and have a good catalytic performance. Our findings not only pave the way for incorporating the POM clusters into polymers with well-defined structures and high molecular weights, but also offer a competitive strategy for developing more novel catalytic systems by introducing the poly(polyoxometalate)s.

Twining Poly(polyoxometalate) Chains into Nanoropes

“…A few successful examples of POM–polymer hybrid preparation are now given. 1) Hybrid catalysts have been prepared by covalently decorating the surface of a macroporous resin with POM clusters or by integrating the clusters into a polymer backbone as side groups . The advantage of these hybrids is that they not only maintain the catalytic function of the POM group, but also that they have the benefits of facile recovery and reuse.…”

“…Herein, we report further studies on the aggregation of the hybrid poly(polyoxometalate) [poly(POM)] that was synthesised in our previous study . It is constructed from a polynorbornene backbone and POM cluster pendants linked by a short spacer.…”

Bottom‐Up Hybridization: A Strategy for the Preparation of a Thermostable Polyoxometalate–Polymer Hybrid with Hierarchical Hybrid Structures

“…We selected inorganic polyoxometalates (POMs) and organic polymers as building blocks to construct POM-polymer hybrid materials. [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] In the specific design of a POM-polymer hybrid molecule, a Wells-Dawson-type POM cluster was used as the inorganic building block because it could be covalently modified, [29] and the organic block was commercially available poly(ethylene glycol) (PEG). [7,8] Organic polymers were selected for their ease of processability and attractive mechanical properties.…”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…75) [360,361], nucleic acid bases attached to an aminoethylglycine support [362], alkoxyquinoline groups (e.g. 77) [363], fluorescent groups and PEG groups (copolymer) [364]; polyoxometallates [365], dendriditically connected to a polylactate and a polystyrene system [366], and dendritic connection to anthraquinone moieties [367]; (19) bis(norbornenesuccinimide)s connected through a perylene ring [368]; (20) aza-Diels-Alder derived azanorbornenes (e.g. 80) [369]; (21) oxanorbornenes connected to azide groups [370]; (22) oxanorbornenecuccinic anhydride (81) [371]; (23) oxanorbornenesuccinimides, including those connected to alkyne groups [372], and to dendrimeric systems [373,374]; and (24) oxanorbornenedicarboxylate esters connected to guanidine groups [375].…”