Yoan C. Simon

Low-power photon upconversion through triplet–triplet annihilation in polymers

Low-power upconversion via sensitized triplet–triplet annihilation (TTA-UC) is a useful and versatile process that allows for the conversion of optical radiation into photons of higher energy. While this effect had been known to occur in solution for some 50 years, it was only very recently realized for the first time in polymers. The possibility to realize the TTA-UC process in solid materials is important for a variety of applications that range from the optimization of photovoltaic devices to bioimaging. This article provides a brief introduction to the field, summarizes the underlying photophysical aspects, reviews the design concepts for TTA-UC in polymers, and summarizes the recent advances in the development of such materials.

Biosensors Based on Porous Cellulose Nanocrystal–Poly(vinyl Alcohol) Scaffolds

Cellulose nanocrystals (CNCs), which offer a high aspect ratio, large specific surface area, and large number of reactive surface groups, are well suited for the facile immobilization of high density biological probes. We here report functional high surface area scaffolds based on cellulose nanocrystals (CNCs) and poly(vinyl alcohol) (PVA) and demonstrate that this platform is useful for fluorescence-based sensing schemes. Porous CNC/PVA nanocomposite films with a thickness of 25-70 nm were deposited on glass substrates by dip-coating with an aqueous mixture of the CNCs and PVA, and the porous nanostructure was fixated by heat treatment. In a subsequent step, a portion of the scaffolds hydroxyl surface groups was reacted with 2-(acryloxy)ethyl (3-isocyanato-4-methylphenyl)carbamate to permit the immobilization of thiolated fluorescein-substituted lysine, which was used as a first sensing motif, via nucleophile-based thiol-ene Michael addition. The resulting sensor films exhibit a nearly instantaneous and pronounced change of their fluorescence emission intensity in response to changes in pH. The approach was further extended to the detection of protease activity by immobilizing a Förster-type resonance energy transfer chromophore pair via a labile peptide sequence to the scaffold. This sensing scheme is based on the degradation of the protein linker in the presence of appropriate enzymes, which separate the chromophores and causes a turn-on of the originally quenched fluorescence. Using a standard benchtop spectrometer to monitor the increase in fluorescence intensity, trypsin was detected at a concentration of 250 μg/mL, i.e., in a concentration that is typical for abnormal proteolytic activity in wound fluids.

Organogels for low-power light upconversion

We herein report new organogels that permit efficient optical upconversion (UC) by triplet–triplet annihilation. The materials studied consist of a liquid organic phase, composed of a mixture of N,N-dimethylformamide and dimethyl sulfoxide in which the UC chromophore pair Pd(II) mesoporphyrin IX and 9,10-diphenylanthracene was dissolved, and a three-dimensional polymer network formed by covalently cross-linking poly(vinyl alcohol) with hexamethylene diisocyanate. The new gels are highly transparent, shape-persistent, and display efficient green-to-blue upconversion with UC quantum yields of >0.6 and 14% under ambient and oxygen-free conditions, respectively. The design approach presented here permits the fabrication of a hitherto unexplored class of materials with a unique combination of properties. The framework can easily be extended to other materials based on other solvents, polymer networks, and/or chromophore pairs.

Low-power upconversion in dye-doped polymer nanoparticles.

Examples of nanoscale low-power upconverting systems are rapidly increasing because of their potential application in numerous areas such as bioimaging or drug delivery. The fabrication of dye-doped cross-linked rubbery nanoparticles that exhibit upconversion even at relatively low power densities is reported here. The nanoparticles were prepared by surfactant-free emulsion polymerization of n-butylacrylate with divinylbenzene as a cross-linker, followed by dyeing of the resulting particles with a two-chromophore system composed of a palladium porphyrin sensitizer, and diphenylanthracene. Blue emission (≈440 nm) of these systems was observed upon excitation at 532 nm. In addition to their optical properties, the particles were characterized by electron microscopy and dynamic light scattering.

Mechano- and Thermoresponsive Photoluminescent Supramolecular Polymer

Mechanoresponsive luminescent (MRL) materials change their emission color upon application of external forces. Many dyes with MRL behavior are known, but they normally do not display useful mechanical properties. Here, we introduce a new approach to overcome this problem, which relies on combining MRL compounds with the concept of supramolecular polymerization. As a first embodiment, a cyano-substituted oligo(p-phenylenevinylene), whose MRL behavior is associated with different solid-state assemblies, was derivatized with two ureido-4-pyrimidinone groups, which support the formation of a dynamic supramolecular polymer. The new material displays the thermomechanical characteristics of a supramolecular polymer glass, offers three different emission colors in the solid state, and exhibits both MRL and thermoresponsive luminescent behavior.

Low-power photon upconversion in organic glasses

Green-to-blue upconverting molecular glasses consisting of a metal octaethylporphyrin (MOEP, M = Pd, Pt) sensitizer and 9-(4-hydroxymethylphenyl)-10-phenyl anthracene (DPA-CH2OH) as an emitter are reported. In these materials, incident light is transformed into higher-energy radiation by way of triplet–triplet annihilation upconversion. The DPA-CH2OH–MOEP mixtures form transparent glasses when cooled from the thermally stable melt, even at rates as low as 1 °C min−1. In a systematic study, the PdOEP concentration was varied from 0.025 to 6.6 mol%. The normalized upconverted light intensity decreased with increasing sensitizer concentration by almost three orders of magnitude, as a result of sensitizer aggregation. The upconverted light intensity also decreased upon deliberate crystallization of the upconverting materials. Beyond demonstrating the first embodiment of upconversion in molecular glasses, the results highlight the importance of morphology control in solid-state upconverting materials.

Melt-processed polymer glasses for low-power upconversion via sensitized triplet–triplet annihilation

The process of low-power light upconversion by triplet–triplet annihilation is well established in solutions of appropriate sensitizer–emitter pairs, but has only recently been reduced to practice in polymeric materials. Here, the fabrication of upconverting glasses based on poly(methyl methacrylate) (PMMA), palladium octaethylporphyrin (PdOEP, sensitizer, 0.005–0.5% w/w relative to the polymer) and large amounts of diphenylanthracene (DPA, emitter, 25% w/w relative to the polymer) is reported. These materials were produced by compression-molding pre-mixed blends and subsequently quenching the samples in a molecularly mixed state. The resulting films upconvert green incident light (543 nm) of low incident power density (34 mW cm−2) into blue light (440 nm). The dependence of the upconversion intensity on the sensitizer concentration was studied and the results suggest that an optimal composition range exists, where the upconversion efficiency is maximal.

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.

Light upconversion by triplet–triplet annihilation in diphenylanthracene-based copolymers

Low-power light upconversion by triplet–triplet annihilation (TTA-UC) was only recently achieved in glassy materials. Here, a new strategy based on covalent tethering of diphenylanthracene (DPA) emitters to a polymeric backbone is reported. The design aims to optimize the efficiency of this photophysical process in glassy polymeric materials by increasing the emitter content. To that end, DPA molecules were covalently attached to a methacrylate-type monomer and further copolymerized with methylmethacrylate (MMA). Green-to-blue (543 to 440 nm) upconversion was observed at power densities as low as 32 mW cm−2 in films prepared by solution casting and compression molding (co)polymers containing 8–72 wt% of DPA and palladium octaethyl porphyrin (PdOEP) as a sensitizer (0.03–0.7 wt%). The upconversion intensity was studied as a function of DPA and PdOEP contents and the results suggest that upconversion is optimal for DPA and PdOEP weight fractions of 34 and 0.05 wt% respectively.

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.