Photochemical [2 + 2]-cycloadditions store solar energy in chemical bonds and efficiently access strained organic molecular architectures. Functionalized [3]-ladderdienes undergo 2]-photocycloadditions to afford cubanes, a class of molecules. The substituents (e.g., methyl, trifluoromethyl, cyclopropyl) affect the overall reactivities these cubane precursors; yields range from 1 48%. However, origin substituent effects on chemoselectivities is not understood. We now integrate single...

Photoswitches are molecules that undergo a reversible, structural isomerization after exposure to certain wavelengths of light. The dynamic control offered by molecular photoswitches is favorable for materials chemistry, photopharmacology, and catalysis applications. Ideal absorb visible light have long-lived metastable isomers. We used high-throughput virtual screening predict the absorption maxima (λmax) E-isomer half-life (t1/2) Z-isomer. However, computing photophysical kinetic...

Molecular photoswitches use light to interconvert from a thermodynamically stable isomer into metastable isomer. Photoswitches have been used in photopharmacology, catalysis, and molecular solar thermal (MOST) materials because of their spatiotemporal activation. Visible-light-absorbing are especially attractive low-energy minimizes undesired photochemical reactions enables biological applications. Ideal require well-separated absorption spectra for both isomers long-lived states. However,...

Azoarene photoswitches are versatile molecules that interconvert from their E-isomer to Z-isomer with light. Azobenzene is a prototypical photoswitch but its derivatives can be poorly suited for in vivo applications such as photopharmacology due undesired photochemical reactions promoted by ultraviolet light and the relatively short half-life (t1/2) of (2 days). Experimental computational studies suggest these properties (λmax E isomer t1/2 Z-isomer) inversely related. We identified isomeric...

Azoarenes are an important class of molecular photoswitches that often undergo E → Z isomerization with ultraviolet light and have short Z-isomer lifetimes. Azobenzene has been a widely studied photoswitch for decades but can be poorly suited photopharmacological applications due to its UV-light absorption short-lived half-life (t1/2). Recently, diazo one or more thiophene rings in place phenyl ring emerged as promising candidates, they exhibit stable photostationary state (98% conversion)...

Gas-evolving photochemical reactions use light and mild conditions to access strained organic compounds irreversibly. Cyclopropenones are a class of light-responsive molecules used in bioorthogonal photoclick reactions; their excited-state decarbonylation reaction mechanisms misunderstood due ultrafast (<100 femtosecond) lifetimes. We have combined multiconfigurational quantum mechanical (QM) calculations non-adiabatic molecular dynamics (NAMD) simulations uncover the mechanism...

Molecular photoswitches use light to interconvert from a thermodynamically stable isomer into meta-stable isomer. Chemists and materials scientists have applied in photopharmacology, catalysis, molecular solar thermal (MOST) materials. Visible-light-absorbing are attractive because the relatively low-energy minimizes undesired photochemical reactions enables biological applications. Designing ideal requires long-lived metastable states; predicting their half-lives with theory is difficult it...

Photochemical [2+2]-photocycloadditions are used to efficiently access strained organic molecular architectures, storing solar energy in chemical bonds. Functionalized [3]-ladderenes have been shown undergo afford cubanes, an energy-dense class of molecules. The substituents (e.g., methyl, trifluoromethyl, and cyclopropyl) affect the overall reactivities these cubane precursors leading a yield from 1% 48%. We now integrate single multireference calculations our machine-learning-accelerated...

The cyclopropane ring features prominently in active pharmaceuticals, and this has spurred the development of synthetic methodologies that effectively incorporate highly strained motif into such molecules. As such, elegant solutions to prepare densely functionalized cyclopropanes, particularly ones embedded within core complex structures, have become increasingly sought-after. Here we report stereospecific synthesis a set cyclopropanes with vicinal quaternary stereocenters via solvent-free...

Azoarenes are an important class of molecular photoswitches that often undergo E➝Z isomerization with ultraviolet light and have short Z-isomer lifetimes. We performed density functional theory calculations [PBE0-D3BJ/6-31+G(d,p)] on 26 hemi-azothiophenes provided design principles for azoarenes featuring red-shifted E-isomer absorption (λmax) long half-lives (t1/2). Our top candidate has λmax a t1/2 approaching 360 nm 279 years, respectively.

Gas-evolving photochemical reactions use mild conditions to access strained organic compounds irreversibly. Cyclopropenones are a class of pseudo-aromatic light-responsive molecules used in bioorthogonal photoclick reactions; their excited-state decarbonylation reaction mechanisms misunderstood due ultrafast (&lt;100 femtosecond) lifetimes. We have combined state-of-the-art multiconfigurational quantum mechanical (QM) calculations and non-adiabatic molecular dynamics (NAMD) simulations...

Photochemical [2+2]-photocycloadditions are used to efficiently access strained organic molecular architectures, storing solar energy in chemical bonds. Functionalized [3]-ladderenes have been shown undergo afford cubanes, an energy-dense class of molecules. The substituents (e.g., methyl, trifluoromethyl, and cyclopropyl) affect the overall reactivities these cubane precursors leading a yield from 1% 48%. We now integrate single multireference calculations our machine-learning-accelerated...

Photoswitches are molecules that undergo a reversible, structural isomerization after exposure to different wavelengths of light. The dynamic control offered by molecular photoswitches is favorable for applications in materials chemistry, photopharmacology, and catalysis. Ideal absorb visible light have long-lived metastable isomers. We used high throughput virtual screening predict the absorption maxima (λmax) E-isomer half-lives (t1/2) Z-isomer. However, computing photophysical kinetic...

Molecular photoswitches use light to interconvert from a thermodynamically stable isomer into meta-stable isomer. Chemists and materials scientists have applied in photopharmacology, catalysis, molecular solar thermal (MOST) materials. Visible-light-absorbing are attractive because the relatively low-energy minimizes undesired photochemical reactions enables biological applications. Designing ideal requires long-lived metastable states; predicting their half-lives with theory is difficult it...

Azoarene photoswitches are versatile molecules that interconvert from their E-isomer to Z-isomer with light. Azobenzene is a prototypical photoswitch but its derivatives can be poorly suited for in vivo applications such as photopharmacology due undesired photochemical reactions promoted by ultraviolet light and relatively short half-life (t1/2) of the (2 days). Experimental computational studies suggest these properties (λmax E isomer t1/2 Z-isomer) inversely related. We identified isomeric...