The Rise and Current Status of Polaritonic Photochemistry and Photophysics.

The interaction between molecular electronic transitions and electromagnetic fields can be enlarged to the point where distinct hybrid light-matter states, polaritons, emerge. The photonic contribution to these states results in increased complexity as well as an opening to modify the photophysics and photochemistry beyond what normally can be seen in organic molecules. It is today evident that polaritons offer opportunities for molecular photochemistry and photophysics, which has caused an ever-rising interest in the field. Focusing on the experimental landmarks, this review takes its reader from the advent of the field of polaritonic chemistry, over the split into polariton chemistry and photochemistry, to present day status within polaritonic photochemistry and photophysics. To introduce the field, the review starts with a general description of light-matter interactions, how to enhance these, and what characterizes the coupling strength. Then the photochemistry and photophysics of strongly coupled systems using Fabry-Perot and plasmonic cavities are described. This is followed by a description of room-temperature Bose-Einstein condensation/polariton lasing in polaritonic systems. The review ends with a discussion on the benefits, limitations, and future developments of strong exciton-photon coupling using organic molecules.

Interplay between Polaritonic and Molecular Trap States.

Strong exciton-photon coupling exhibits the possibility to modify the photophysical properties of organic molecules. This is due to the introduction of hybrid light-matter states, called polaritons, which have unique physical and optical properties. Those strongly coupled systems provide altered excited-state dynamics in comparison to the bare molecule case. In this study, we investigate the interplay between polaritonic and molecular trap states, such as excimers. The molecules used in this study show either prompt or delayed emission from trap states. For both cases, a clear dependency on the exciton-photon energy tuning was observed. Polaritonic emission gradually increased with a concurrent removal of aggregation-induced emission when the systems were tuned toward lower energies. For prompt emission, it is not clear whether the experimental results are best explained by a predominant relaxation toward the lower polariton after excitation or by a direct excimer to polariton transition. However, for the delayed emission case, trap states are formed on the initially formed triplet manifold, making it evident that an excimer-to-polariton transition has occurred. These results unveil the possibility to control the trap state population by creating a strongly coupled system, which may form a mitigation strategy to counteract detrimental trap states in photonic applications.

Effect of the Aza-N-Bridge and Push-Pull Moieties: A Comparative Study between BODIPYs and Aza-BODIPYs.

In the field of fluorescent dyes, difluoroboron-dipyrromethenes (BODIPY) have a highly respected position. To predict their photophysical properties prior to synthesis and therefore to successfully design molecules specifically for one's needs, a solid structure-function understanding based on experimental observations is vital. This work delivers a photophysical evaluation of BODIPY and aza-BODIPY derivatives equipped with different electron-withdrawing/-donating substituents. Using combinatorial chemistry, pyrroles substituted with electron-donating/-withdrawing substituents were condensed together in two different manners, thus providing two sets of molecules. The only difference between the two sets is the bridging unit providing a so far lacking comparison between BODIPYs and aza-BODIPYs structural homologues. Replacing the meso-methine bridge with an aza-N bridge results in a red-shifted transition and considerably different, temperature-activated, excited-state relaxation pathways. The effect of electron-donating units on the absorption but not emission for BODIPYs was suppressed compared to aza-BODIPYs. This result could be evident in a substitution pattern-dependent Stokes shift. The outlook of this study is a deeper understanding of the structure-optics relationship of the (aza)-BODIPY-dye class, leading to an improvement in the de novo design of tailor-made molecules for future applications.

A fine-tuned azobenzene for enhanced photopharmacology in vivo.

Despite the power of photopharmacology for interrogating signaling proteins, many photopharmacological systems are limited by their efficiency, speed, or spectral properties. Here, we screen a library of azobenzene photoswitches and identify a urea-substituted "azobenzene-400" core that offers bistable switching between cis and trans with improved kinetics, light sensitivity, and a red-shift. We then focus on the metabotropic glutamate receptors (mGluRs), neuromodulatory receptors that are major pharmacological targets. Synthesis of "BGAG12,400," a photoswitchable orthogonal, remotely tethered ligand (PORTL), enables highly efficient, rapid optical agonism following conjugation to SNAP-tagged mGluR2 and permits robust optical control of mGluR1 and mGluR5 signaling. We then produce fluorophore-conjugated branched PORTLs to enable dual imaging and manipulation of mGluRs and highlight their power in ex vivo slice and in vivo behavioral experiments in the mouse prefrontal cortex. Finally, we demonstrate the generalizability of our strategy by developing an improved soluble, photoswitchable pore blocker for potassium channels.

Correction: Strong light-matter interactions: a new direction within chemistry.

Correction for 'Strong light-matter interactions: a new direction within chemistry' by Manuel Hertzog et al., Chem. Soc. Rev., 2019, 48, 937-961, DOI: 10.1039/C8CS00193F.

Entropic Mixing Allows Monomeric-Like Absorption in Neat BODIPY Films.

Intermolecular interactions play a crucial role in materials chemistry because they govern thin film morphology. The photophysical properties of films of organic dyes are highly sensitive to the local environment, and a considerable effort has therefore been dedicated to engineering the morphology of organic thin films. Solubilizing side chains can successfully spatially separate chromophores, reducing detrimental intermolecular interactions. However, this strategy is also significantly decreasing achievable dye concentration. Here, five BODIPY derivatives containing small alkyl chains in the α-position were synthesized and photophysically characterized. By blending two or more derivatives, the increase in entropy reduces aggregation and therefore produces films with extreme dye concentration and, at the same time almost solution like absorption properties. Such a film was placed inside an optical cavity and the achieved system was demonstrated to reach the strong exciton-photon coupling regime by virtue of the achieved dye concentration and sharp absorption features of the film.

Strong light-matter interactions: a new direction within chemistry.

It is possible to modify the chemical and physical properties of molecules, not only through chemical modifications but also by coupling molecules strongly to light. More intriguingly, strong coupling between molecules and light is possible even without the presence of a photon. The phenomenon that makes this possible is called vacuum fluctuations, which is the finite zero point energy of the quantized electromagnetic field inside an optical cavity. The light-matter coupling, which can be as large as 1 eV (100 kJ mol-1), leads to the formation of new hybrid states, called polaritons. The formed hybrid states can be viewed as a linear combination of light (vacuum field) and matter (molecules), thus completely changing the energy landscape of the system. Using vacuum fluctuations, strong light-matter interactions have for instance been used to change chemical reactivity, charge conductivity, excited state relaxation pathways and rates of chemical reactions of organic molecules. In this review a brief history of the field is given, followed by a theoretical framework, methods of analysis, and a review of accomplishments. Finally, a personal reflection on the future perspectives and applications within this field is given.

Angle-Independent Polariton Emission Lifetime Shown by Perylene Hybridized to the Vacuum Field Inside a Fabry-Pérot Cavity.

The formation of hybrid light-matter states in optical structures, manifested as a Rabi splitting of the eigenenergies of a coupled system, is one of the key effects in quantum optics. The hybrid states (exciton polaritons) have unique chemical and physical properties and can be viewed as a linear combination of light and matter. The optical properties of the exciton polaritons are dispersive by nature, a property inherited from the photonic contribution to the polariton. On the other hand, the polariton lifetime in organic molecular systems has recently been highly debated. The photonic contribution to the polariton would suggest a lifetime on the femtosecond time scale, much shorter than experimentally observed. Here, we increase the insights of light-mater states by showing that the polariton emission lifetime is nondispersive. A perylene derivative was strongly coupled to the vacuum field by incorporating the molecule into a Fabry-Pérot cavity. The polariton emission from the cavity was shown to be dispersive, but the emission lifetime was nondispersive and on the time scale of the bare exciton. The results were rationalized by the exciton reservoir model, giving experimental evidence to currently used theories, thus improving our understanding of strong coupling phenomena in molecules.