Strong coupling plays a significant role in influencing chemical reactions and tuning material properties by modifying the energy landscapes of the systems. Here we study the effect of vibrational strong coupling (VSC) on supramolecular organization. For this purpose, a rigid-rod conjugated polymer known to form gels was strongly coupled together with its solvent in a microfluidic IR Fabry-Perot cavity. Absorption and fluorescence studies indicate a large modification of the self-assembly under such cooperative VSC. Electron microscopy confirms that in this case, the supramolecular morphology is totally different from that observed in the absence of strong coupling. In addition, the self-assembly kinetics are altered and depend on the solvent vibration under VSC. The results are compared to kinetic isotope effects on the self-assembly to help clarify the role of different parameters under strong coupling. These findings indicate that VSC is a valuable new tool for controlling supramolecular assemblies with broad implications for the molecular and material sciences.

Porous conjugated polymers are synthesized by metal-catalyzed coupling reactions. The progress for porous polymers when planar or tetrahedral building blocks are connected by alkyne units into novel materials is highlighted. The most prominent reaction for the buildup of the microporous alkyne-bridged polymers is the Sonogashira reaction, connecting alkynes to aromatic iodides or bromides. The availability of the building blocks and the potency of the Sonogashira reaction allow preparing a large variety of intrinsically porous polymeric materials, in which rigid struts connect multipronged centers. The microporous polymers are used as catalysts and as storage materials for gases and sensors. Postfunctionalization schemes, understanding of structure-property relationships, and the quest for high porosity are pertinent.

We report two hyperbranched conjugated polymers (HCP) with truxene units as core and 1,4-didodecyl-2,5-diethynylbenzene as well as 1,4-bis(dodecyloxy)-2,5-diethynylbenzene as comonomers. Two analogous poly(para-phenyleneethynylene)s (PPE) are also prepared as comparison to demonstrate the difference between the truxene and the phenyl moieties in their optical properties and their sensing performance. The four polymers are tested for nitroaromatic analytes and display different fluorescence quenching responses. The quenching efficiencies are dependent upon the spectral overlap between the absorbance of the analyte and the emission of the fluorescent polymer. Optical fingerprints are obtained, based on the unique response patterns of the analytes toward the polymers. With this small sensor array, one can distinguish nine nitroaromatic analytes with 100% accuracy. The amphiphilic polymer F127 (a polyethylene glycol-polypropylene glycol block copolymer) carries the hydrophobic HCPs and self-assembles into micelles in water, forming highly fluorescent HCP micelles. The micelle-bound conjugated polymers detect nitroaromatic analytes effectively in water and show an increased sensitivity compared to the sensing of nitroaromatics in organic solvents. The nitroarenes are also discriminated in water using this four-element chemical tongue.

Solutions of dialkoxy- and dialkyl-poly­(p-phenyleneethynylene)­s (PPE) form well-defined solid state gels by diffusion of a nonsolvent (SOG), even if the concentration of the PPEs is only 2.5 mg/mL. The residual solvent in the SOG gel does not contain any dissolved PPE according to fluorescence and emissive lifetime measurements. The solvent inside of the gels is confirmed to be more than 90% of the polar solvent, which gives temperature stability to the gel and makes it available for infiltration of analytes, etc. This is in strong contrast to “classic” gels that form by thermal gelation; these still contain dissolved PPE chains. As a result, an ionic-liquid-filled PPE gel could be formed successfully by solvent exchange.

due to the critical impact on their optoelectronic properties. [2] One example is gels composed of π-conjugated molecules (π-gels). [3] π-Gels are nanocomposites that comprise branched fibers and enclosed solvents. In the fibers, π-conjugated molecules typically assume polycrystalline ordering. Since the charge transport in organic semiconductors is governed by intermolecular interactions, the high crystallinity of π-gels provides preferable electronic properties. π-Gels have been applied to a variety of electronic devices including organic field-effect transistors (OFETs). [4] These supramolecular devices display improved performance in comparison to that of bulk devices. However, integrating supramolecular assemblies into a device still remains elusive, that is, transforming a gel to a device often results in sparsely dispersed fibers. Although individual molecular assemblies display remarkable charge-carrier mobility, the transconductance (g m = ∂I d /∂V g) and the output current by the device unit are far below the practically desired values. Recently, we comprehensively studied the gelation behavior of poly(para-phenyleneethynylene)s (PPEs) and disclosed a