A series of hybrid supramolecular star polymers (SSPs) consisting of a polyoxometalate EuW₁₀O₃₆^9? (EuW₁₀) core and different length of polystyrene arms have been fabricated by a “core-first” method, in which the anionic EuW₁₀clusters were firstly encapsulated by cationic molecules with trithioester terminal groups and subsequently polystyrene arms were grafted by reversible addition–fragmentation chain-transfer (RAFT) polymerization. The SSPs exhibit structurally dependent self-assembly behaviours in solution, at the air–water interface and solid state. It was found that the SSPs with short arms form large assemblies with a diameter over 100 nm in chloroform, while those with long arms tend to be mono-dispersed. Meanwhile, the distance between the EuW₁₀cores of adjacent SSPs in Langmuir monolayers and casting films can be precisely adjusted by PS arms, which leads to a tunable colour purity of EuW₁₀luminescence. This tight structure–property relationship enables the polyoxometalate-cored SSPs to act as potential building blocks for the construction of hybrid polymer materials with controllable functions.

http://pubs.rsc.org/en/Content/ArticleLanding/2013/PY/c3py01349a#!divAbstract