A novel co-assembly based on the block copolymer bearing photocleavable groups and macroanionic polyoxometalates Na9[Ln(W5O18)2] (LnW10, Ln = Eu, Dy) triggered by UV light is realized in aqueous solution. The copolymer synthesized by atom transfer radical polymerization (ATRP) undergoes irreversible cleavage upon UV irradiation to generate primary amine (pKa ≈ 8–9) residues which are completely protonated under a neutral pH in aqueous solution. Electrostatic attractions between the resulting positively charged copolymers and anionic LnW10 drive the formation of assemblies. In situ small angle X-ray scattering and transmission electron microscopy are used to characterize the morphology of the assemblies. The microenvironments around polyoxometalates in the core of hybrid assemblies become highly hydrophobic, resulting in dramatically enhanced photoluminescence with the obvious intensity enhancement. The solution parameters pH and salt additives show great effects on the formation of assemblies.

A new type of supramolecular chemosensor based on the polyoxometalate (POM) Na9DyW10O36 (DyW10) and the block copolymer poly(ethylene oxide-b-N,N-dimethylaminoethyl methacrylate) (PEO114-b-PDMAEMA16) is reported. By taking advantage of the CO2 sensitivity of PDMAEMA blocks to protonate the neutral tertiary amino groups, CO2 can induce the electrostatic coassembly of anionic DyW10 with protonated PDMAEMA blocks, and consequently trigger the luminescence chromism of DyW10 due to the change in the microenvironment of Dy3+. The hybrid complex in dilute aqueous solution is very sensitive to CO2 content and shows rapid responsiveness in luminescence. The luminescence intensity of the DyW10/PEO-b-PDMAEMA complex increases linearly with an increasing amount of dissolved CO2, which permits the qualitative and quantitative detection of CO2. The complex solution also shows good selectivity for CO2, with good interference tolerance of CO, N2, HCl, H2O and SO2. The supramolecular chemosensor can be recycled through disassembly of the hybrid complex by simply purging with inert gases to remove CO2.

A series of multicolor luminescent hybrid materials based on three primary molecular pixel components, isostructural lanthanide-containing inorganic clusters LnW10, i.e. red-emissive Na9EuW10O36 (EuW10) and green-emissive Na9TbW10O36 (TbW10), and a blue-emissive small organic molecule quinine were constructed in a general and straightforward way. The neutral-cationic block copolymer poly(ethylene oxide)114-b-poly(2-(2-guanidinoethoxy)ethyl methacrylate)23 (PEO114-b-PGu23) electrostatically co-assembles with the inorganic clusters LnW10 into micelles, and consequently effectively prohibits the energy transfer between LnW10 and quinine. Three luminescent elements possessing independent emission properties in supramolecular assemblies, like molecular pixels, were deeply investigated for the first time. On the basis of additive color theory, fluent emitting color changes within the triangle enclosed by the luminophores in the chromatic diagram were achieved at diverse mixing ratios and exciting wavelengths with precise prediction and convenient reproduction.

The hybrid assembled materials based on redox-active polyoxometalates H3PMo12O40·nH2O and the neutral–cationic block copolymers poly(ethylene oxide-block-N,N-dimethylaminoethyl methacrylate) in aqueous solution were constructed through electrostatic interactions. Triggered by photochemical or electrochemical methods, the charge number of the redox-active polyoxometalates charged in situ, which not only induced the chromisity of the solution, but also driven diverse morphologies of the assembly. The assembly morphologies could be switched between spherical micelles and wormlike micelles after extra stimuli. Both of chromic and assembling processes are reversible and repeatable. Moreover, the hybrid materials improve the processability of the inorganic cluster polyoxometalates which maintains its original chromic properties at the same time. This simple strategy put a general way to fabricate smart stimuli-responsive polyoxometalates-based functional materials with potential applications in optical switches, biosensors, detectors and electrochromic devices. The variety of the ionic inorganic clusters and polyelectrolytes offered a broaden platform to enrich the electrostatic-motivated assembling and expand their applications.

Hybrid hydrogels based on electrostatic co-assembly of polyoxometalates and ABA triblock copolymers were readily prepared and exhibit excellent luminescence and self-healing performance.

A unique type of novel supramolecular hybrid hydrogel based on the co-assembly of the anionic polyoxometalate and the cationic ABA triblock copolymer via electrostatic interaction was reported to show jellyfish-like switchable chromic luminescence. The hydrogel undergoes reversible sol–gel transition in response to pH changes, and simultaneously exhibits an unprecedented luminescent chromism from weak green to strong white.

A novel fused acceptor–donor–acceptor (A–D–A) type panchromatically electrochromic compound was synthesized. It exhibited intensive absorption bands covering entire UV–vis and near-infrared regions upon reduction to the radical anionic state, owing to the simultaneous presence of π*−π* transitions and intervalence charge transfer.

Novel well-defined diblock copolymers polystyrene-b-poly[benzoic acid N′-(4-vinylbenzoyl)hydrazide dinuclear ruthenium complex] (PSm-b-P(DCH-Ru)n, m = 2076, n = 417, 1024, 2432) are synthesized through two-step sequential nitroxide-mediated radical polymerization (NMRP) and postpolymerization complexation. The block copolymers containing pendant dinuclear ruthenium groups possess an amphiphilic nature. The assembly behavior of the complex block copolymers in both selective solvents acetonitrile and dioxane at various initial concentrations and block compositions were characterized by transimission electron microscopy (TEM). Spherical micelles and vesicles were observed in acetonitrile and dioxane, respectively. The photoluminescent, electrochemical, and spectroelectrochemical properties of the complex block copolymers in solution were investigated. The solvatochromism in the UV–vis region and electrochromism (EC) in the near-infrared region (NIR) were observed. Aggregates solutions in either acetonitrile or dioxane show quite different electroptical properties from that of the homogeneous solution in DMF, which might be due to spatial-confinement effect of the functional Ru pendent groups in core–shell nanostructures.

Hybrid hydrogels based on electrostatic co-assembly of polyoxometalates and ABA triblock copolymers were readily prepared and exhibit excellent luminescence and self-healing performance.

A new type of supramolecular chemosensor based on the polyoxometalate (POM) Na9DyW10O36 (DyW10) and the block copolymer poly(ethylene oxide-b-N,N-dimethylaminoethyl methacrylate) (PEO114-b-PDMAEMA16) is reported. By taking advantage of the CO2 sensitivity of PDMAEMA blocks to protonate the neutral tertiary amino groups, CO2 can induce the electrostatic coassembly of anionic DyW10 with protonated PDMAEMA blocks, and consequently trigger the luminescence chromism of DyW10 due to the change in the microenvironment of Dy3+. The hybrid complex in dilute aqueous solution is very sensitive to CO2 content and shows rapid responsiveness in luminescence. The luminescence intensity of the DyW10/PEO-b-PDMAEMA complex increases linearly with an increasing amount of dissolved CO2, which permits the qualitative and quantitative detection of CO2. The complex solution also shows good selectivity for CO2, with good interference tolerance of CO, N2, HCl, H2O and SO2. The supramolecular chemosensor can be recycled through disassembly of the hybrid complex by simply purging with inert gases to remove CO2.

A unique type of novel supramolecular hybrid hydrogel based on the co-assembly of the anionic polyoxometalate and the cationic ABA triblock copolymer via electrostatic interaction was reported to show jellyfish-like switchable chromic luminescence. The hydrogel undergoes reversible sol–gel transition in response to pH changes, and simultaneously exhibits an unprecedented luminescent chromism from weak green to strong white.