Twining Poly(polyoxometalate) Chains into Nanoropes. Issue 58 (13th September 2019)

• Record Type: Journal Article
• Authors: Zhang, Lan‐Lan; Miao, Wen‐Ke; Ren, Li‐Jun; Yan, Yu‐Kun; Lin, Yue; Wang, Wei
• Is Part Of: Chemistry. Volume 25:Issue 58(2019)
• Page Start: 13396
• Page End: 13401
• Publication Date: 2019-09-13
• Subjects: aggregation -- nanostructures -- polyoxometalates -- polymers -- supramolecular chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201902875
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Organic polymers and inorganic clusters belong to two different disciplines and have completely different properties and structures. When a cluster is attached to the backbone of a polymer as a pendant, the resultant hybrid polymers (polyclusters) exhibit unique behaviours totally different from those of conventional polymers owing to the nanoscale size of the cluster and its particular interactions. Herein, the aggregation of a poly(polyoxometalate)—a polynorbornene backbone with inorganic polyoxometalate cluster pendants—upon addition of a non‐solvent to its dilute solution is reported. A three‐dimensional network of tangled and snake‐like nanothreads was observed. Direct visualisation of individual nanoscale clusters enabled identification of single chains within the nanothreads. These observations suggest that during the process of aggregation, the hybrid polymer forms curved or extended chains as a consequence of an armouring effect in which the collapsed cluster pendants wrap around the backbone. The collapse occurs because they become less soluble in the solvent/non‐solvent mixture. The extended chains then become entwined and form nanoropes consisting of multiple chains wound around each other. This study provides a deeper understanding of the nature of polyclusters and should also prove useful for their future development and application. Abstract : Showing the ropes : Nanoropes of a poly(polyoxometalate) [poly(POM)], that is, a polynorbornene backbone with pendant polyoxometalate clusters, are created by twining multiple extended poly(POM) chains in solution. Identification of single POM clusters by high‐angle annular dark‐field scanning transmission electron microscopy verified formation of the nanoropes (see figure).