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This account highlights the role of restricted bond rotations in influencing the excited-state reactivity of organic molecules. It highlights the photochemical reactivity of various organic molecules and the design strategies that could be exploited by chemists to utilize restricted bond rotations to uncover new excited-state reactivity and to achieve selectivity.1 Introduction.2 NEER-Principle and Restricted Bond Rotations in the Excited State3 [2+2]-Photocycloaddition of Enamides4 [3+2]-Photocycloaddition vs. Paternò–Büchi Reaction of Enamides5 Divergent Photoreactivity of Enones Dictated by Restricted Bond Rotations: Norrish–Yang reactions vs. 6π-Photocyclization6 Divergent Photoreactivity of Imides with Alkenes: [2+2]-Photocycloaddition vs. Photoene Reaction7 Summary and Outlook

Photodegradable, recyclable, and renewable, crosslinked polymers from bioresources show promise towards developing a sustainable strategy to address the issue of plastics degradability and recyclability. Photo processes are not widely exploited for upcycling polymers in spite of the potential to have spatial and temporal control of the degradation in addition to being a green process. In this report we highlight a methodology in which biomass-derived crosslinked polymers can be programmed to degrade at ≈300 nm with ≈60 % recovery of the monomer. The recovered monomer was recycled back to the crosslinked polymer.

An unprecedented and previously unknown photochemical reactivity of 1,3-dicarbonyl compounds is observed with amino-alkenes leading to dihydropyrans. This novel photochemical reactivity changes the established paradigm related to the De Mayo reaction between 1,3-dicarbonyl compounds and alkenes. This new reaction allows convenient access to the Marmycin core in a single step from commercially available reactants. The origin and scope of this new photoreaction is detailed with preliminary photophysical and mechanistic investigations.

This feature article highlights the role of different hydrogen bonding templates in enhancing and controlling excited state processes with an eye towards the development of Brønsted acid mediated organo-photocatalysts for asymmetric photochemical transformations.

Photoreaction of enamides tethered to a phenyl ketone leads to either [3+2]-photocycloaddition or Paterno-Buchi reaction. This divergence in chemical reactivity originating from the same excited state was dependent on the reaction temperature. At low temperatures the Paterno-Buchi reaction was preferred, whereas at higher temperatures there was preference toward formation of [3+2]-photoproduct.

Direct activation of H-phosphine oxide to react with an unsaturated carbon-carbon bond is a straightforward approach for accessing alkenylphosphine oxides, which shows significant applications in both synthetic and material fields. However, expensive metals and strong oxidants are typically required to realize the transformation. Here, we demonstrate the utility of earth-abundant cobaloxime to convert H-phosphine oxide into its reactive radical species under visible light irradiation. The radical species thus generated can be utilized to functionalize alkenes and alkynes without any external photosensitizer and oxidant. The coupling with terminal alkene generates

Regiodivergent photocyclization of dearomatized acylphloroglucinol substrates has been developed to produce type A polycyclic polyprenylated acylphloroglucinol (PPAP) derivatives using an excited-state intramolecular proton transfer (ESIPT) process. Using this strategy, we achieved the enantioselective total syntheses of the type A PPAPs (-)-nemorosone and (-)-6-epi-garcimultiflorone A. Diverse photocyclization substrates have been investigated leading to divergent photocyclization processes as a function of tether length. Photophysical studies were performed, and photocyclization mechanisms were proposed based on investigation of various substrates as well as deuterium-labeling experiments.

Glutaraldehyde (GA) is the most common biocide used in unconventional oil and gas production. Photocatalytic degradation of GA in brine simulating oil and gas produced water using Ag/AgCl/BiOCl composite as a photocatalyst with visible light was investigated. Removal of GA at 0.1 mM in 200 g/L NaCl solution at pH 7 was 90% after 75 min irradiation using 5 g/L of the photocatalyst. The GA removal followed pseudo-first order reaction with a rate constant of 0.0303 min−1. At pH 5 or at 300 g/L NaCl, the photocatalytic removal of GA was almost completely inhibited. Similar inhibitions were observed when adding dissolved organic carbon (from humic acid) at 10 and 200 mg/L, or Br− at 120 mg/L to the system. The removal rate of GA markedly increased with increasing pH (5–9), photocatalyst loading (2–8 g/L) and under 350 nm UV (compared to visible light). On the contrary, the removal rate of GA markedly decreased with increasing NaCl and initial GA concentrations (0–300 g/L for NaCl and 0.1–0.4 mM for GA). A quenching experiment was also conducted; electron holes (h+) and superoxide ( ) were found as the main reactive species responsible for the removal of GA while OH had a very limited effect.

This review highlights the excited state characteristics of imines and processes that govern their photochemical and photophysical properties. This review examines the pathways for deactivation and types of photochemical reactions that originate from excited imines. This review also features recent strategies that are developed to circumvent the fundamental issues that have plagued the development of the aza Paterno–Buchi reaction.

The textbook photoreaction between two alkenes is the [2 + 2]-photocycloaddition resulting in functionalized cyclobutanes. Herein, we disclose an unusual reactivity of alkenes that favor photoene reaction over the [2 + 2]-photocycloaddition.

Biobased photoacids were synthesized from naturally occurring vanillin analogues and evaluated for their photoacidity. It was determined that substituted ortho-vanillin possessed the strongest acidity in the excited state.

Conjugate addition occurs efficiently from excited hydrazide based acrylanilides under both UV and metal free visible light irradiations. The reaction proceeds via an excited state encounter complex that bifurcates either via an electron or energy transfer pathway. The generality of excited state conjugate addition is demonstrated using chloromethylation and by thiol addition.

Selective excited-state intramolecular proton-transfer (ESIPT) photocycloaddition of 3-hydroxyflavones with trans, trans-1,4-diphenyl-1,3-butadiene is described. Using this methodology, total syntheses of the natural products (±)-foveoglin A and (±)-perviridisin B were accomplished. Enantioselective ESIPT photocycloaddition using TADDOLs as chiral hydrogen-bonding additives provided access to (+)-foveoglin A. Mechanistic studies have revealed the possibility for a photoinduced electron-transfer (PET) pathway.

Endoxifen is the main active metabolite of a common cytostatic drug, tamoxifen. Endoxifen has been recently detected in the final effluent of municipal wastewater treatment plants. The antiestrogenic activity of endoxifen could bring negative effects to aquatic life if released to the water environment. This study elucidated the fate and susceptibility of (E)- and (Z)-endoxifen (2 μg mL−1, 1:1 wt ratio between the two easily interchangeable isomers) in wastewater and receiving surface water to sunlight. Phototransformation by-products (PBPs) and their toxicity were determined. Sunlight reduced at least 83% of endoxifen concentration in wastewater samples, whereas in surface water samples, 60% of endoxifen was photodegraded after 180 min of the irradiation. In ultrapure water samples spiked with endoxifen, PBPs were mainly generated via con-rotatory 6π-photocyclization, followed by oxidative aromatization. These PBPs underwent secondary reactions leading to a series of PBPs with different molecular weights. Eight PBPs were identified and the toxicity analysis via the Toxicity Estimation Software Tool revealed that seven of these PBPs are more toxic than endoxifen itself. This is likely due to the formation of poly-aromatic core in the PBPs due to exposure to sunlight. Therefore, highly toxic PBPs may be generated if endoxifen is present in water and wastewater exposed to sunlight. The presence, fates and activities of these PBPs in surface water especially at locations close to treated wastewater discharge points should be investigated.

Intramolecular atropselective aza Paterno–Buchi reaction involving atropisomeric enamide and imine functionalities under sensitized irradiation leads to azetidine products in good yield and selectivity (ee >96 %). A mechanistic model based on detailed photophysical and isomerization kinetic studies is provided that shed light into the reactivity of enamides leading to aza Paterno–Buchi reaction.

The popularity and variety of bio-based polymers are increasing as the chemical industry identifies and develops commercial biomass alternatives for traditional petroleum-based products. Environmental impacts and renewability of novel biochemical processes or materials must be determined in a quantitative manner to support sustainable development. A life cycle assessment (LCA) model was constructed for programmed photodegradation of polymeric/oligomeric materials derived from renewable bioresources. This research evaluates the sustainability for the production of 2,5-furandicarboxylic acid (FDCA), a polymer building block, from 5-hydroxymethylfurfural (HMF), an intermediate derived from renewable resource fructose. A phototrigger is attached to the monomers during the polymerization process, resulting in a polymer that degrades in the presence of UV light. The LCA results indicate that 38–49% of environmental impacts were attributed to the conversion of FDCA to polymer, where electricity consumption and use of non-renewable chemicals such as dichloromethane and other solvents were significant contributors. The process of recycling of polymeric material reduced all environmental impacts, suggesting that recycling outweighs the impacts caused by the production of phototriggers.

Most traditional photoreactions require UV light to yield the desired product. To address this issue, photoreaction of hydrazide based chromophores was evaluated with visible light using a metal free photocatalyst to afford photoproducts in high yields. This hydrazide functionality itself may be removed/modified after the photoreaction, highlighting its role as a "photo-auxiliary". A preliminary mechanistic model based on photophysical experiments is provided to highlight the generality of the strategy.

Thiazine dyes such as thionine, methylene blue and methylene green were exchanged within monovalent cation exchanged Y zeolites. Depending on the water content the dye molecules exist as either monomer (‘dry’) or dimer (‘wet’). The monomeric dye is effective in producing singlet oxygen by energy transfer process inside the zeolite cavity. In polar zeolites like LiY, NaY energy transfer predominates whereas in basic zeolites like CsY electron transfer overtakes the energy transfer leading to the photo-destruction of the dye. While on short time of irradiation, energy transfer to oxygen led to selectivity in the product distribution, but on prolonged irradiation, destruction of the dye through electron transfer was the main outcome.

Photochemical transformations are a powerful tool in organic synthesis to access structurally complex and diverse synthetic building blocks. However, this great potential remains untapped in the mainstream synthetic community due to the challenges associated with stereocontrol originating from excited state(s). The finite lifetime of an excited state and nearly barrierless subsequent processes present significant challenges in manipulating the stereochemical outcome of a photochemical reaction. Several methodologies were developed to address this bottleneck including photoreactions in confined media and preorganization through noncovalent interactions resulting in stereoenhancement. Yet, stereocontrol in photochemical reactions that happen in solution in the absence of organized assemblies remained largely unaddressed. In an effort to develop a general and reliable methodology, our lab has been exploring non-biaryl atropisomers as an avenue to perform asymmetric phototransformations. Atropisomers are chiral molecules that arise due to the restricted rotation around a single bond (chiral axis) whose energy barrier to rotation is determined by nonbonding interactions (most often by steric hindrance) with appropriate substituents. Thus, atropisomeric substrates are chirally preorganized during the photochemical transformation and translate their chiral information to the expected photoproducts. This strategy, where "axial to point chirality transfer" occurs during the photochemical reaction, is a hybrid of the successful Curran's prochiral auxiliary approach involving atropisomers in thermal reactions and the Havinga's NEER principle (nonequilibrating excited-state rotamers) for photochemical transformations. We have investigated this strategy in order to probe various aspects such as regio-, enantio-, diastereo-, and chemoselectivity in several synthetically useful phototransformations including 6π-photocyclization, 4π-ring closure, Norrish-Yang photoreactions, Paternò-Büchi reaction, and [2 + 2]- and [5 + 2]-photocycloaddition. The investigations detailed in this Account clearly signify the scope of our strategy in accessing chirally enriched products during phototransformations. Simple design modifications such as tailoring the steric handle in atropisomers to hold reactive units resulted in permanently locked/traceless axial chirality in addition to incorporating multiple stereocenters in already complex scaffolds obtained from phototransformation. Further improvements allowed us to employ low energy visible light rather than high energy UV light without compromising the stereoenrichment in the photoproducts. Continued investigations on atropisomeric scaffolds have unraveled new design features, with outcomes that are unique and unprecedented for excited state reactivity. For example, we have established that reactive spin states (singlet or triplet excited state) profoundly influence the stereochemical outcome of an atropselective phototransformation. In general, the photochemistry and photophysics of atropisomeric substrates differ significantly from their achiral counterparts irrespective of having the same chromophore initiating the excited state reactivity. The ability of axially chiral chromophores to impart stereoenrichment in the intramolecular photoreactions appears to be promising. A challenging endeavor for the "axial to point chirality transfer" strategy is to enhance stereoenrichment or alter chemical reactivity in intermolecular photoreactions. Insights gained from our investigations will serve as a platform to venture into more complicated yet fruitful research in terms of broad synthetic utility.

Hydrazides derivatives were evaluated to understand the role of N−N bond in dictating the outcome of photoreactions in the solid state.

Regiodivergent photocyclization of dearomatized acylphloroglucinol substrates has been developed to produce type A polycyclic polyprenylated acylphloroglucinol (PPAP) derivatives using an excited-state intramolecular proton transfer (ESIPT) process. Using this strategy, we achieved the enantioselective total syntheses of the type A PPAPs (−)-nemorosone and (−)-6-epi-garcimultiflorone A. Diverse photocyclization substrates have been investigated leading to divergent photocyclization processes as a function of tether length. Photophysical studies were performed and photocyclization mechanisms were proposed based on investigation of various substrates as well as deuterium-labeling experiments.

We have prepared a core-shell magnetic silica-coated hydroxyapatite, Fe₃O₄@SiO₂@HAp composite materials for pH-responsive drug delivery applications. Captopril (Cap) and ibuprofen (Ibu) were chosen as model hydrophilic and hydrophobic drugs, respectively. The drugs were encapsulated into the Fe₃O₄@SiO₂@HAp composite via electrostatic interactions with existing amine and carboxylic acid groups during calcium phosphate shell formation. The formation of calcium phosphate shell not only protects the encapsulated drugs from leaching but also controls the release rate of drugs from the composite system depending on various pH conditions. We have tested the release behavior of Cap and Ibu drugs under different pH conditions such as neutral pH (pH 7.4) and acidic pH (pH 5.0), respectively. The study result reveals that the synthesized Fe₃O₄@SiO₂@HAp composite is suitable for release of both water soluble and water insoluble drugs based on a pH-responsive controlled manner.

Atropisomeric enone-imides and enone-amides featuring N-CAryl bond rotation were evaluated for intramolecular [2 + 2] photocycloaddition. Straight addition product was observed over cross-addition product with good control over reactivity. The atropselectivity was found to be dependent on the substituent on the aryl ring. Substitution-dependent atropselectivity was rationalized on the basis of a divergent mechanistic pathway.

Photochemistry, bearing significant applications in natural and man-made events such as photosynthesis, vision, photolithography, photodynamic therapy, etc., is yet to become a common tool during the synthesis of small molecules in a laboratory. Among other rationale, the inability to influence photochemical reactions with temperature, solvent, additives, etc., dissuades chemists from employing light-initiated reactions as a routine synthetic tool. This review highlights how diverse, highly organized structures such as solvent-free crystals and water-soluble host-guest assemblies can be employed to control and manipulate photoreactions and thereby serve as an efficient tool for chemists, including those interested in synthesis. The efficacy of the media in modifying the excited-state behavior of organic molecules is illustrated with photocycloaddition in general and [2 + 2] photocycloaddition in particular, reactions widely employed in the synthesis of complex natural products as well as highly constrained molecules, as exemplars. The reaction media, highly pertinent in the context of green sustainable chemistry, include solvent-free crystals and solids such as silica, clay, and zeolite and water-soluble hosts that can solubilize and preorganize hydrophobic reactants in water. Since no other reagent would be more sustainable than light and no other medium greener than water, we believe that the supramolecular photochemistry expounded here has a momentous role as a synthetic tool in the future.

Mechanistic investigations of the intermolecular [2+2] photocycloaddition of coumarin with tetramethylethylene mediated by thiourea catalysts reveal that the reaction is enabled by a combination of minimized aggregation, enhanced intersystem crossing, and altered excited-state lifetime(s). These results clarify how the excited-state reactivity can be manipulated through catalyst-substrate interactions and reveal a third mechanistic pathway for thiourea-mediated organo-photocatalysis.

We report a novel, ambient pressure, continuous gas-phase, synthesis of Si-QDs by direct pyrolysis of cyclohexasilane (CHS, Si6H12), a liquid hydrosilane. We also report that using a low activation energy precursor such as Si6H12 enabled effective gas-phase reduction of the hydrosilane leading to better nucleation of Si nanoparticles than other hydrosilanes. By suitably designing the reactor length and its temperature profile, the structure of the Si-QDs are rendered amorphous or crystalline. The as-synthesized Si-QDs were thermally hydrosilylated with 1-dodecene and their properties examined. High resolution transmission electron microscopic (HRTEM) analysis revealed that the nano-crystalline Si-QDs (Si-NCs) have an average size of 2.0 nm. The amorphous Si-QDs (a-Si-QDs) and the Si-NCs samples exhibited UV-Vis absorptions below 300 and 375 nm, respectively. The a-Si-QDs and Si-NCs excited at 300 nm showed PL emissions at ∼370 nm and 374 nm, respectively, while the latter showed additional characteristic emissions at 403, 425 and 457 nm. The quantum yields were determined to be 9 and 13%, respectively, with PL relaxation life times of 6.5 and 13 ns, respectively.

Endoxifen is an effective metabolite of a common chemotherapy agent, tamoxifen. Endoxifen, which is toxic to aquatic animals, has been detected in wastewater treatment plant (WWTP) effluent. This research investigates ultraviolet (UV) radiation (253.7 nm) application to degrade (E)- and (Z)-endoxifen in water and wastewater and phototransformation by-products (PBPs) and their toxicity. The effects of light intensity, pH and initial concentrations of (E)- and (Z)-endoxifen on the photodegradation rate were examined. Endoxifen in water was eliminated ≥99.1% after 35 s of irradiation (light dose of 598.5 mJ cm−2). Light intensity and initial concentrations of (E)- and (Z)-endoxifen exhibited positive trends with the photodegradation rates while pH had no effect. Photodegradation of (E)- and (Z)-endoxifen in water resulted in three PBPs. Toxicity assessments through modeling of the identified PBPs suggest higher toxicity than the parent compounds. Photodegradation of (E)- and (Z)-endoxifen in wastewater at light doses used for disinfection in WWTPs (16, 30 and 97 mJ cm−2) resulted in reductions of (E)- and (Z)-endoxifen from 30 to 71%. Two of the three PBPs observed in the experiments with water were detected in the wastewater experiments. Therefore, toxic compounds are potentially generated at WWTPs by UV disinfection if (E)- and (Z)-endoxifen are present in treated wastewater.

Glutaraldehyde (GA) has been used extensively as a biocide in hydraulic fracturing fluid leading to its presence in oil and gas produced water. In this study, photolysis was used to degrade GA from brine solutions simulating produced water. Photolysis of GA was performed under ultraviolet (UV) irradiation. GA can be photolyzed by UV at all studied conditions with the efficiency ranging from 52 to 85% within one hour irradiation. Photolysis of GA followed pseudo-first order kinetics. A photolysis rate constant of GA at 0.1 mM in 200 g/L of salt at pH 7 was 0.0269 min−1 with a quantum yield of 0.0549 under 224 W illumination. The degradation rate of GA increased with increasing incident light intensity and decreasing pH. Increasing initial GA concentration resulted in decreasing degradation rate of GA. The degradation of GA was affected by salt concentration. At lower salt concentrations, notable retardation of GA photodegradation rate was observed while at higher salt concentrations GA photodegradation was improved compared to those without salt. OH was more dominant in sample without salt than sample with salt suggesting different photolytic mechanisms, indirect and direct photolysis, respectively. Oligomers were identified as the main photoproducts of GA photolysis.

This review highlights the use of atropisomeric (axially chiral) chromophores for stereospecific photoreactions. The presence of axial chirality in the substrate imparts excellent stereo (enantio- ...