Donor-Acceptor Stenhouse Adducts: Exploring the Effects of Ionic Character.

The effects of solution-state dielectric and intermolecular interactions on the degree of charge separation provide a route to understanding the switching properties and concentration dependence of donor-acceptor Stenhouse adducts (DASAs). Through solvatochromic analysis of the open-form DASA in conjunction with X-ray diffraction and computational theory, we have analyzed the ionic character of a series of DASAs. First- and third-generation architectures lead to a higher zwitterionic resonance contribution of the open form and a zwitterionic closed form, whereas the second-generation architecture possesses a less charge-separated open form and neutral closed form. This can be correlated with equilibrium control and photoswitching solvent compatibility. As a result of the high contribution of the zwitterionic resonance forms of first- and third-generation DASAs, we were able to control their switching kinetics by means of ion concentration, whereas second-generation DASAs were less affected. Importantly, these results show how the previously reported concentration dependence of DASAs is not universal, and that DASAs with a more hybrid structure in the open form can achieve photoswitching at high concentrations.

Unusual concentration dependence of the photoisomerization reaction in donor-acceptor Stenhouse adducts.

Donor-acceptor Stenhouse adducts comprise a new class of reversible photochromic molecules that absorb in the visible and near-infrared spectral regions. Unimolecular photoisomerization reactions are usually assumed to be insensitive to photochrome density, at least up to millimolar concentrations. In this paper, the photoisomerization kinetics of a third-generation donor-acceptor Stenhouse adduct molecule (denoted DASA) are examined over a range of concentrations. DASA switches efficiently at micromolar concentrations in both liquid solution and in polymers, but as the photochrome concentration is increased there is a dramatic inhibition of the photoisomerization. A kinetic study of both the reactant and photoproduct decays at varying concentrations and in different hosts indicates that the forward photoisomerization and the thermal backward reaction can change by factors of 20 or more depending on DASA concentration. Femtosecond transient absorption experiments show that the initial cis → trans step of the isomerization is not affected by concentration. It is hypothesized that long-range coulombic interactions interfere with the ground state electrocyclization stage of the isomerization, which is unique to the DASA family of photochromes. The physical origin of the inhibition of photoswitching at high photochrome concentrations must be understood if the DASA class of molecules is to be used for applications that require high photochrome concentrations, including photomechanical actuation.

Tunable Photothermal Actuation Enabled by Photoswitching of Donor-Acceptor Stenhouse Adducts.

We report a visible light-responsive bilayer actuator driven by the photothermal properties of a unique molecular photoswitch: donor-acceptor Stenhouse adduct (DASA). We demonstrate a synthetic platform to chemically conjugate DASA to a load-bearing poly(hexyl methacrylate) (PHMA) matrix via Diels-Alder click chemistry that enables access to stimuli-responsive materials on scale. By taking advantage of the negative photochromism and switching kinetics of DASA, we can tune the thermal expansion and actuation performance of DASA-PHMA under constant light intensity. This extends the capabilities of currently available responsive soft actuators for which mechanical response is determined exclusively by light intensity and enables the use of abundant broadband light sources to trigger tunable responses. We demonstrate actuation performance using a visible light-powered cantilever capable of lifting weight against gravity as well as a simple crawler. These results add a new strategy to the toolbox of tunable photothermal actuation by using the molecular photoswitch DASA.

Direct introduction of nitrogen and oxygen functionality with spatial control using copper catalysis.

Synthetic chemists have spent considerable effort optimizing the synthesis of nitrogen and oxygen containing compounds through a number of methods; however, direct introduction of N- and O-functionality remains challenging. Presented herein is a general method to allow for the simultaneous installation of N- and O-functionality to construct unexplored N-O heterocyclic and amino-alcohol scaffolds. This transformation uses earth abundant copper salts to facilitate the formation of a carbon-centered radical and subsequent carbon-nitrogen bond formation. The intermediate aminoxyl radical is terminated by an intramolecularly appended carbon-centered radical. We have exploited this methodology to also access amino-alcohols with a range of aliphatic and aromatic linkers.