Dictating Photoreactivity through Restricted Bond Rotations: Cross-Photoaddition of Atropisomeric Acrylimide Derivatives under UV/Visible-Light Irradiation

Nonbiaryl atropisomeric acrylimides underwent facile [2 + 2] photocycloaddition leading to cross-cyclobutane adducts with very high stereospecificity (enantiomeric excess (ee): 99% and diastereomeric excess (de): 99%). The photoreactions proceeded smoothly in isotropic media for both direct and triplet sensitized irradiations. The reactions were also found to be very efficient in the solid state where the same cross-cyclobutane adduct was observed. Photophysical studies enabled us to understand the excited-state photochemistry of acrylimides. The triplet energy was found to be ∼63 kcal/mol. The reactions proceeded predominantly via a singlet excited state upon direct irradiation with very poor intersystem crossing that was ascertained by quantification of the generated singlet oxygen. The reactions progressed smoothly with triplet sensitization with UV or visible-light irradiations. Laser flash photolysis experiments established the triplet transient of atropisomeric acrylimides with a triplet lifetime at room temperature of ∼40 ns

Photochemical Reactivity of dTPT3: A Crucial Nucleobase Derivative in the Development of Semisynthetic Organisms

In 2017, the Romesberg group successfully developed the dTPT3·dNaM unnatural base pair to create a semisynthetic organism with enhanced genetic fidelity and the ability to store additional genetic information indefinitely. It is also desirable that the newly developed genetic material remains stable upon exposure to radiation. However, the photochemical properties of dTPT3 are presently unknown. In this contribution, excitation of dTPT3 with near-visible radiation is shown to efficiently populate a reactive triplet state in high yield and on a sub-1 ps time scale; a state that is able to survive for up to a few microseconds in aqueous solution. The triplet state can also generate singlet oxygen in ca. 30% yield, suggesting that dTPT3 can act as a pervasive photosensitizer to accelerate oxidatively generated damage within DNA and to other biological molecules within cells

2,4-Dithiothymine as a Potent UVA Chemotherapeutic Agent

Substitution of both oxygen atoms in the exocyclic carbonyl groups of the thymine chromophore by sulfur atoms results in a remarkable redshift of its absorption spectrum from an absorption maximum at 267 nm in thymidine to 363 nm in 2,4-dithiothymine (Δ<i>E</i> = 9905 cm^–1). A single sulfur substitution of a carbonyl group in the thymine chromophore at position 2 or 4 results in a significantly smaller redshift in the absorption maximum, which depends sensitively on the position at which the sulfur atom is substituted, varying from 275 nm in 2-thiothymine to 335 nm in 4-thiothymidine. Femtosecond transient absorption spectroscopy reveals that excitation of 2,4-dithiothymine at 335 or 360 nm leads to the ultrafast population of the triplet state, with an intersystem crossing lifetime of 180 ± 40 fsthe shortest intersystem crossing lifetime of any DNA base derivative studied so far in aqueous solution. Surprisingly, the degree and position at which the sulfur atom is substituted have important effects on the magnitude of the intersystem crossing rate constant, showing a 1.2-, 3.2-, and 4.2-fold rate increases for 2-thiothymine, 4-thiothymidine, and 2,4-dithiothymine, respectively, relative to that of thymidine, whereas the triplet yield increases 60-fold to near unity, independent of the site of sulfur atom substitution. While the natural thymine monomers owe their high degree of photostability to ultrafast internal conversion to the ground state and low triplet yields, the near-unity triplet yields in the thiothymine series account for their potent photosensitization properties. Nanosecond time-resolved luminescence spectroscopy shows that 4-thiothymidine and 2,4-dithiothymine are efficient singlet oxygen generators, with singlet oxygen quantum yields of 0.42 ± 0.02 and 0.46 ± 0.02, respectively, in O₂-saturated acetonitrile solution. Taken together, these photophysical measurements strongly suggest that 2,4-dithiothymine can act as a more effective UVA chemotherapeutic agent than the currently used 4-thiothymidine, especially in deeper-tissue chemotherapeutic applications

Photoinitiated Metal-Free Controlled/Living Radical Polymerization Using Polynuclear Aromatic Hydrocarbons

Photoinitiated metal-free controlled living radical polymerization of (meth)­acrylates, and vinyl monomers was investigated using the polynuclear aromatic compounds pyrene and anthracene. Fluorescence spectral analyses along with nuclear magnetic resonance studies were performed to determine the rate constants of initiator radical formation and to investigate the mechanisms of polymerization. The obtained polymers were analyzed by spectral and chromatographic methods. Results show that the excited state anthracene undergoes a faster electron transfer reaction with the alkyl halide initiator than the excited state of pyrene. Pyrene excimers, which are formed at higher concentrations, also react with alkyl halides to form initiator radicals. Although pyrene monomers and excimers are acting slower, polymers with higher control over the chain end functionalities and molecular weight characteristics are obtained in comparison to anthracene as sensitizer

CIDEP from a Polarized Ketone Triplet State Incarcerated within a Nanocapsule to a Nitroxide in the Bulk Aqueous Solution

Thioxanthone and benzil derivatives were incarcerated into an octa acid nanocapsule. Photoexcitation of these ketones generated electronic triplet excited states, which become efficiently quenched by positively charged nitroxides adsorbed outside on the external surface of the negatively charged nanocapsule. Although the triplet excited ketone and quencher are separated by a molecular wall (nanocapsule), quenching occurs on the nanosecond time scale and generates spin-polarized nitroxides, which were observed by time-resolved EPR spectroscopy. Because opposite signs of spin polarization of nitroxides were observed for thioxanthone and benzil derivatives, it is proposed that the electron spin polarization transfer mechanism of spin-polarized triplet states to nitroxides is the major mechanism of generating nitroxide polarization

Mechanisms by which Alkynes React with CpCr(CO)₃H. Application to Radical Cyclization

The reaction of CpCr­(CO)₃H with activated alkynes in benzene has been examined. The kinetics of these reactions have been studied with various alkynes, along with the stereochemistry with which the alkynes are hydrogenated. The hydrogenation of phenyl acetylene and diphenyl acetylene with CpCr­(CO)₃H has been shown to occur by a hydrogen atom transfer (HAT) mechanism. The reaction of CpCr­(CO)₃H with dimethyl acetylenedicarboxylate (DMAD) produced hydrogenated products as well as phenyl substitution from reaction with solvent. On the basis of kinetic data, it is thought that the reaction of DMAD may proceed via a single electron transfer (SET) as the rate-determining step. The radical anion of dimethylfumarate was observed by EPR spectroscopy during the course of the reaction, supporting this claim. The aromatic 1,6 eneyne (<b>8</b>) gave cyclized products in 78% yield under catalytic conditions (35 psi H₂), presumably by the 5-exo-trig cyclization of the vinyl radical arising from H• transfer. Using a cobaloxime catalyst (<b>12</b>) hydrogenation was completely eliminated to yield 100% cyclized products

Mechanisms by which Alkynes React with CpCr(CO)₃H. Application to Radical Cyclization

The reaction of CpCr­(CO)₃H with activated alkynes in benzene has been examined. The kinetics of these reactions have been studied with various alkynes, along with the stereochemistry with which the alkynes are hydrogenated. The hydrogenation of phenyl acetylene and diphenyl acetylene with CpCr­(CO)₃H has been shown to occur by a hydrogen atom transfer (HAT) mechanism. The reaction of CpCr­(CO)₃H with dimethyl acetylenedicarboxylate (DMAD) produced hydrogenated products as well as phenyl substitution from reaction with solvent. On the basis of kinetic data, it is thought that the reaction of DMAD may proceed via a single electron transfer (SET) as the rate-determining step. The radical anion of dimethylfumarate was observed by EPR spectroscopy during the course of the reaction, supporting this claim. The aromatic 1,6 eneyne (<b>8</b>) gave cyclized products in 78% yield under catalytic conditions (35 psi H₂), presumably by the 5-exo-trig cyclization of the vinyl radical arising from H• transfer. Using a cobaloxime catalyst (<b>12</b>) hydrogenation was completely eliminated to yield 100% cyclized products

Electron Spin Polarization Transfer from a Nitroxide Incarcerated within a Nanocapsule to a Nitroxide in the Bulk Aqueous Solution

A thioxanthone derivative containing a covalently attached ¹⁵N-labeled nitroxide was incarcerated into an octaacid nanocapsule. Photoexcitation of the thioxanthone chromophore generated electron spin polarization of the nitroxide. This spin polarization of the ¹⁵N-labeled nitroxide was transferred through the walls of the carcerand to a ¹⁴N-labeled nitroxide in external bulk solvent, a process that was directly observed by time-resolved EPR spectroscopy. The efficiency of the communication between the incarcerated guest and molecules in the bulk solvent was shown to be controlled by supramolecular factors such as Coulombic attraction and repulsion between the guest@host complex and charged molecules in the bulk solvent phase

Photoinduced Electron Transfer Reactions of Highly Conjugated Thiophenes for Initiation of Cationic Polymerization and Conjugated Polymer Formation

Photoinduced electron transfer reactions of highly conjugated thiophene derivatives, 4,7-di­(2,3-dihydrothieno­[3,4-<i>b</i>]­[1,4]­dioxin-5-yl)­benzo­[1,2,5]­thiadiazole (DTDT) and 5,8-bis­(2,3-dihydrothieno­[3,4-<i>b</i>]­[1,4]­dioxin-5-yl)-2,3-di­(thiophen-2-yl)­quinoxaline (DTDQ), with diphenyl­iodonium hexafluorophosphate (Ph₂I⁺PF₆^–) and triphenylsulfonium hexafluorophosphate (Ph₃S⁺PF₆^–) were investigated by laser flash photolysis, fluorescence and phosphorescence spectroscopy, and polymerization studies. High fluorescence quantum yields, long fluorescence lifetimes (∼10 ns in aprotic solvents), and absence of detectable phosphorescence at 77 K for both compounds indicate inefficient intersystem crossing into the triplet state and dominant role of singlet excited state. Photolysis of DTDT or DTDQ in the presence of iodonium salt with visible light results in the formation of radical cations of DTDT and DTDQ as detected by laser flash photolysis. Sulfonium salts do not undergo such electron transfer reactions due to the unfavorable redox potentials. The importance of the described photoinduced electron transfer process with respect to the initiation of cationic polymerization and formation of conjugated polymers was demonstrated

Tailoring Atropisomeric Maleimides for Stereospecific [2 + 2] PhotocycloadditionPhotochemical and Photophysical Investigations Leading to Visible-Light Photocatalysis

Atropisomeric maleimides were synthesized and employed for stereospecific [2 + 2] photocycloaddition. Efficient reaction was observed under direct irradiation, triplet-sensitized UV irradiation, and non-metal catalyzed visible-light irradiation, leading to two regioisomeric (<i>exo</i>/<i>endo</i>) photoproducts with complete chemoselectivity (exclusive [2 + 2] photoproduct). High enantioselectivity (ee > 98%) and diastereoselectivity (dr > 99:1%) were observed under the employed reaction conditions and were largely dependent on the substituent on the maleimide double bond but minimally affected by the substituents on the alkenyl tether. On the basis of detailed photophysical studies, the triplet energies of the maleimides were estimated. The triplet lifetimes appeared to be relatively short at room temperature as a result of fast [2 + 2] photocycloaddition. For the visible-light mediated reaction, triplet energy transfer occurred with a rate constant close to the diffusion-limited value. The mechanism was established by generation of singlet oxygen from the excited maleimides. The high selectivity in the photoproduct upon reaction from the triplet excited state was rationalized on the basis of conformational factors as well as the type of diradical intermediate that was preferred during the photoreaction