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.
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ACS Macro Lett
January 2025
Department of Chemical Engineering, Key Laboratory of Advanced Materials (MOE), Tsinghua University, Beijing 100084, China.
The microcapsule-containing self-reporting system has attracted attention for its excellent characteristics in visualizing microdamage. In this study, we developed self-reporting materials based on the formation of donor-acceptor Stenhouse adducts (DASA) from microcapsules containing Meldrum's acid furfural conjugate (MAFC). Under mechanical force, MAFC is released from broken microcapsules and forms highly colored DASA with secondary amines in the matrix to indicate the small cracks or deformations.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Loker Hydrocarbon Research Institute, University of Southern California, Los Angeles, California 90089, United States.
The development of photoswitches that absorb low energy light is of notable interest due to the growing demand for smart materials and therapeutics necessitating benign stimuli. Donor-acceptor Stenhouse adducts (DASAs) are molecular photoswitches that respond to light in the visible to near-infrared spectrum. As a result of their modular assembly, DASAs can be modified at the donor, acceptor, triene, and backbone heteroatom molecular compartments for the tuning of optical and photoswitching properties.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Univ. Bordeaux, CNRS, Bordeaux INP, Institut des Sciences Moléculaires, UMR 5255, F-33400 Talence, France.
The effect of conformational dynamics and solvent interactions on the second-order nonlinear optical (NLO) responses of the open and closed forms of a donor-acceptor Stenhouse adduct (DASA) are investigated by a mixed quantum/classical computational approach, which couples molecular dynamics (MD) simulations and time-dependent density functional theory (TD-DFT) calculations. The latter are further combined with various solvation schemes, including polarizable continuum models, hybrid QM/MM approaches using either non polarizable or polarizable electrostatic embedding, and QM/QM' schemes with explicit treatment of a few molecules of the first solvation shell. The performances of the different solvation models are discussed in the context of comparisons with experimental data obtained from hyper-Rayleigh scattering measurements.
View Article and Find Full Text PDFNanoscale
December 2024
Institute of Physics of the National Academy of Sciences of Ukraine, 46 Nauki ave., Kyiv, 03028, Ukraine.
We present the spontaneous isomerization of donor-acceptor Stenhouse adducts anchored onto a gold surface, visualized using scanning tunneling spectroscopy. Our investigation reveals a palette of molecular arrangements, including those with ferroelectric-like ordering, evolving over time into a fine pattern consisting of both open and closed forms of the photoswitch.
View Article and Find Full Text PDFMolecules
October 2024
International Joint Laboratory of Biomimetic and Smart Polymers, School of Materials Science and Engineering, Shanghai University, Mailbox 152, Shangda Rd. 99, Shanghai 200444, China.
Mimicking nature, the reversible isomerization of hydrophobic dyes in aqueous solutions is appealing for bio-applications. Here, we report on the reversible isomerization of first-generation solvatochromic donor-acceptor Stenhouse adducts (DASAs) in water within dendritic matrices, realized either through the dendronization of DASAs or the incorporation of DASA pendants into dendronized copolymers. These dendritic macromolecules contain three-fold dendritic oligoethylene glycols (OEGs), which afford the macromolecules water-solubility and unprecedented thermoresponsive behavior.
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