A feasible strategy to achieve large-area mechano-, thermo-and solvatochromic hybrid opal (OPC) and inverse opal photonic crystal (IOPC) films based on polymer hydrogels is described. Silica core particles featuring surface-anchored stimuli-responsive polymers are prepared and advantageously used for the melt-shear organization technique. By this approach hybrid OPC films with adjustable periodicities for photonic applications can be prepared. The large-area OPC films can be furthermore converted into IOPC structures simply by etching the silica particles while maintaining the excellent order of the entire opal film. This herein developed new process seems to be universal and is successfully applied to two thermo-responsive polymers, poly(N-isopropylacrylamide) (PNIPAM) and poly(diethylene glycol methylether methacrylate) (PDEGMEMA) as particle shell materials. Besides the remarkable mechanical robustness of the hybrid OPC and IOPC films, optical properties upon changes of temperature, mechanical stress and different solvents as external triggers are successfully confirmed. The herein described novel strategy for the preparation of inorganic/organic OPC and IOPC polymer films is feasible for a wide range of applications in fields of sensing and photonic band gap materials. † Electronic supplementary information (ESI) available: TEM images, DLS measurements, table of average particle sizes and standard deviations, DSC measurements and additional UV-Vis reection spectra. See

An efficient and universal surface modification protocol for silica nanoparticles is reported for the preparation of novel hybrid optical materials.

Metallopolymers are a unique class of functional materials because of their redox-mediated optoelectronic and catalytic switching capabilities and, as recently shown, their outstanding structure formation and separation capabilities. Within the present study, (tri)block copolymers of poly(isoprene) (PI) and poly(ferrocenylmethyl methacrylate) having different block compositions and overall molar masses up to 328 kg mol are synthesized by anionic polymerization. The composition and thermal properties of the metallopolymers are investigated by state-of-the-art polymer analytical methods comprising size exclusion chromatography, H NMR spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. As a focus of this work, excellent microphase separation of the synthesized (tri)block copolymers is proven by transmission electron microscopy, scanning electron microcopy, energy-dispersive X-ray spectroscopy, small-angle X-ray scattering measurements showing spherical, cylindrical, and lamellae morphologies. As a highlight, the PI domains are subjected to ozonolysis for selective domain removal while maintaining the block copolymer morphology. In addition, the novel metalloblock copolymers can undergo microphase separation on cellulose-based substrates, again preserving the domain order after ozonolysis. The resulting nanoporous structures reveal an intriguing switching capability after oxidation, which is of interest for controlling the size and polarity of the nanoporous architecture.