A mechano- and thermoresponsive luminescent cyclophane

The first fluorescent cyclophane with mechano- and thermoresponsive solid-state fluorescence characteristics is reported. The new cyclophane comprises two 9,10-bis(phenylethynyl)anthracene moieties that are bridged by tetraethylene glycol spacers. The stimuli-responsiveness is based on molecular assembly changes

Mechanochemistry in polymers with supramolecular mechanophores

Mechanochemistry is a burgeoning field of materials science. Inspired by nature, many scientists have looked at different ways to introduce weak bonds into polymeric materials to impart them with function and in particular mechano-responsiveness. In the following sections, the incorporation of some of the weakest bonds, i.e. non- covalent bonds, into polymeric solids is being surveyed. This review covers sequentially π–π interactions, H-bonding and metal-ligand coordination bonds and tries to highlight some of the advantages and limitations of such systems, while providing some key perspective of what may come next in this tantalizing field

Synthesis of poly(sulfonate ester)s by ADMET polymerization

Many hydrocarbon polymers containing heteroatom defects in the main chain have been investigated as degradable polyethylene-like materials, including aliphatic polyesters. Here, acyclic diene metathesis (ADMET) polymerization was used for the synthesis of aliphatic poly(sulfonate ester)s. The requisite sulfonate ester containing α,ω-diene monomers with varying numbers of methylene groups were synthesized, and their polymerization in the presence of ruthenium-N-heterocyclic (Ru-NHC) alkylidene catalysts was studied. A clear negative neighboring group effect (NNGE) was observed for shorter dienes, either inhibiting polymerization or resulting in low- molecular-weight oligomers. The effect was absent when undec-10-en-1-yl undec-10- ene-1-sulfonate was employed as the monomer, and its ADMET polymerization afforded polymers with appreciable number-average molecular weights of up to 37,000 g/mol and a dispersity Đ of 1.8. These polymers were hydrogenated to afford the desired polyethylene-like systems. The thermal and morphological properties of both saturated and unsaturated polymers were investigated. The incorporation of sulfonate ester groups in the polymer backbone offers an interesting alternative to other heteroatoms and helps further the understanding of the effects of these defects on the overall polymer properties

Enhancement of Triplet-Sensitized Upconversion in Rigid Polymers \u3ci\u3evia\u3c/i\u3e Singlet Exciton Sink Approach

To increase the practical usefulness of solid-state sensitized upconversion (UC) materials as components of solar energy harvesting systems, it is important to identify and suppress loss mechanisms, and increase the UC quantum yield (ΦUC). Here we focus on a benchmark UC system consisting of the emitter 9,10-diphenylanthracene (DPA) and the sensitizer platinum octaethylporphyrin (PtOEP) in a rigid poly(methyl methacrylate) (PMMA) matrix, and show that one of the major losses originates from Förster resonant energy transfer (FRET) from DPA back to PtOEP. Even though DPA emission lies within the PtOEP transparency window, the quantitative assessment of singlet exciton diffusion for samples with a high DPA content evidences that long-range FRET results in effective exciton trapping by PtOEP. A dramatic factor-of-6 reduction of the DPA emission quantum yield occurs even at PtOEP concentrations as low as 0.05 wt%. To alleviate this problem, we demonstrate a new concept based on the introduction of highly emissive sink sites to trap the singlet excitons produced upon annihilation prior to their quenching by the sensitizer. For DPA/PtOEP blends in PMMA, 1,6-bis-[2,5-di(dodecyloxyphenyl)ethynyl]pyrene is shown to be a useful sink, which results in 1.5-fold increase of the ΦUC. A maximum ΦUC of 2.7% was achieved, which is among the highest reported values for rigid sensitized UC polymers

Light-responsive azo-containing organogels

While azo compounds are widely employed as radical initiators, they have rarely been used as stimuli-responsive motifs in macromolecular constructs. In this study, an azo-based cross-linker was prepared and reacted with poly(vinyl alcohol) to afford a series of stimuli-responsive organogels. Irradiation of these materials with UV light causes de-cross-linking and triggers a solid-to-liquid phase transition. Model adhesives with de-bonding-on-demand capability based on this design were explored

A Thermo‐ and mechanoresponsive cyano‐substituted oligo(p‐phenylene vinylene) derivative with five emissive states

Multiresponsive materials that display predefined photoluminescence color changes upon exposure to different stimuli are attractive candidates for advanced sensing schemes. Herein, we report a cyano-substituted oligo(p-phenylene vinylene) (cyano-OPV) derivative that forms five different solvent-free solid-state molecular assemblies, luminescence properties of which change upon thermal and mechanical stimulation. Single-crystal X-ray structural analysis suggested that tolyl groups introduced at the termini of solubilizing side-chains of the cyano-OPV play a pivotal role in its solid-state arrangement. Viewed more broadly, this report shows that the introduction of competing intermolecular interactions into excimer-forming chromophores is a promising design strategy for multicolored thermo- and mechanoresponsive luminescent materials

Healable Supramolecular Polymer Solids

The reversible nature of non-covalent interactions between constituting building blocks permits one to temporarily disassemble supramolecular polymers through the application of an appropriate external stimulus “on command”. This framework has recently emerged as a general design strategy for the development of healable polymer systems. The approach exploits that the temporary disassembly decreases the molecular weight and in the case of cross-linked polymers the cross-link density, and thereby causes an increase of the chain mobility and a reduction of the viscosity of the material. The transformation thus enables the disassembled material to flow and fill defects, before the original supramolecular polymer is re-assembled. Focusing on recent progress in the area of healable supramolecular polymer solids based on hydrogen-bonding, metal-ligand and π–π interactions, as well as supramolecular nanocomposites, this review article summarizes the development and current state of the field

Azo-Containing Polymers with Degradation On-Demand Feature

Molecules comprising aliphatic azo moieties are widely used as radical polymerization initiators, but only a few studies have explored their usefulness as stimuli-responsive motifs in macromolecular constructs. The controlled degradation of azo-containing polymers has indeed remained largely unexplored. Here we present the syntheses of linear azo-containing polyamides and polyurethanes and report on their thermally and optically induced responses in solution and the solid state. We show that the stimuli- induced degradation behavior depends strongly on the nature of the polymer backbone, the state of matter, and in solution, on the nature of the solvent. The stimuli-responsive solid-state properties of the azo-containing materials may be particularly useful. In the case of the polyurethanes studied here, temperature- or light-induced cleavage of the azo motifs led to a controllable decrease in the molecular weight, which, in turn, caused a reduction of the elongation at break, modulus, and strength. The controlled degradation of the polymer in well-defined areas can be readily achieved via photopatterning, and this approach was shown to be useful to produce solid structures with graded mechanical properties