Visible Light Photolysis Research Articles

Onium Photocages for Visible-Light-Activated Poly(thiourethane) Synthesis and 3D Printing.

The lack of chemical diversity in light-driven reactions for 3D printing poses challenges in the production of structures with long-term ambient stability, recyclability, and breadth in properties (mechanical, optical, etc.). Herein we expand the scope of photochemistries compatible with 3D printing by introducing onium photocages for the rapid formation of poly(thiourethanes) (PTUs). Efficient nonsensitized visible-light photolysis releases organophosphine and -amine derivatives that catalyze thiol-isocyanate polyaddition reactions with excellent temporal control. Two resin formulations comprising commercial isocyanates and thiols were developed for digital light processing (DLP) 3D printing to showcase the fast production of high-resolution PTU objects with disparate mechanical properties. Onium photocages represent valuable tools to advance light-driven manufacturing of next-generation high-performance sustainable materials.

Anhydrous Carbene Insertion Reactions: A Synthetic Platform for DNA‐Encoded Library

AbstractAn operationally simple anhydrous carbene insertion reaction to construct DNA‐encoded libraries (DEL) is reported. The developed reaction employs visible light photolysis of diazo compounds and Reversible Adsorption to Solid Support (RASS) strategy. From readily available amines, alcohols, phenols, and carboxylic acids, a variety of high‐value molecules, including useful unnatural amino acids, ethers, and esters, promising clinical drug derivatives, and bioactive molecules have been constructed.

Platinum@Hexaniobate Nanopeapods: A Directed Photocatalytic Architecture for Dye-Sensitized Semiconductor H2 Production under Visible Light Irradiation.

Platinum@hexaniobate nanopeapods (Pt@HNB NPPs) are a nanocomposite photocatalyst that was selectively engineered to increase the efficiency of hydrogen production from visible light photolysis. Pt@HNB NPPs consist of linear arrays of high surface area Pt nanocubes encapsulated within scrolled sheets of the semiconductor H x K4-x Nb6O17 and were synthesized in high yield via a facile one-pot microwave heating method that is fast, reproducible, and more easily scalable than multi-step approaches required by many other state-of-the-art catalysts. The Pt@HNB NPPs' unique 3D architecture enables physical separation of the Pt catalysts from competing surface reactions, promoting electron efficient delivery to the isolated reduction environment along directed charge transport pathways that kinetically prohibit recombination reactions. Pt@HNB NPPs' catalytic activity was assessed in direct comparison to representative state-of-the-art Pt/semiconductor nanocomposites (extPt-HNB NScs) and unsupported Pt nanocubes. Photolysis under similar conditions exhibited superior H2 production by the Pt@HNB NPPs, which exceeded other catalyst H2 yields (μmol) by a factor of 10. Turnover number and apparent quantum yield values showed similar dramatic increases over the other catalysts. Overall, the results clearly demonstrate that Pt@HNB NPPs represent a unique, intricate nanoarchitecture among state-of-the-art heterogeneous catalysts, offering obvious benefits as a new architectural pathway toward efficient, versatile, and scalable hydrogen energy production. Potential factors behind the Pt@HNB NPPs' superior performance are discussed below, as are the impacts of systematic variation of photolysis parameters and the use of a non-aqueous reductive quenching photosystem.

Kinetics of chromium(V)-oxo and chromium(IV)-oxo porphyrins: Reactivity and mechanism for sulfoxidation reactions

In this work, chromium(IV)-oxo porphyrins [CrIV(Por)(O)] (2) (Por = porphyrin) were produced either by oxidation of [CrIII(Por)Cl] (1) with iodobenzene diacetate or visible light photolysis of porphyrin‑chromium(III) chlorates. Subsequent oxidation of 2 with silver perchlorate gave chromium(V)-oxo porphyrins [CrV(Por)(O)](ClO4) (3) in three porphyrin ligands, including 5,10,15,20-tetramesitylporphyrin(TMP, a), 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin(TDFPP, b), and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TPFPP, c). Complexes 2 and 3 reacted with thioanisoles to produce the corresponding sulfoxides, and their kinetics of sulfoxidation reactions with a series of aryl methyl sulfides(thioanisoles) were studied in organic solutions. Chromium(V)-oxo porphyrins are several orders of magnitudes more reactive than chromium(IV)-oxo species, and representative second-order rate constants (kox) for the oxidation of thioansole are (0.40 ± 0.01) M−1 s−1 (3a), and (2.82 ± 0.20) × 102 M−1 s−1 (3b), and (2.20 ± 0.01) × 103 M−1 s−1 (3c). The order of reactivity for 2 and 3 follows TPFPP > TDFPP > TMP, in agreement with the electrophilic nature of metal-oxo complexes. Hammett analyses indicate significant charge transfer in the transition states for oxidation of para-substituted thioanisoles by [CrV(Por)(O)]+. The ρ+ constants are −1.69 for 3a, −2.63 for 3b, and − 2.89 for 3c, respectively, mirror values found previously for related metal-oxo species. A mechanism involving the electrophilic attack of the CrV-oxo at sulfides to form a sulfur cation intermediate in the rate-determining step is suggested. Competition studies with chromium(III) porphyrin chloride and PhI(OAc)2 gave relative rate constants for oxidations of competing thioanisoles that closely match ratios of absolute rate constants from chromium(V)-oxo species, which are true oxidants under catalytic conditions.

Nitrogenase Chemistry at 10 Kelvin─Phototautomerization and Recombination of CO-Inhibited α-H195Q Enzyme.

CO-bound forms of nitrogenase are N2-reduction inhibited and likely intermediates in Fischer-Tropsch chemistry. Visible-light photolysis at 7 K was used to interrogate all three known CO-related EPR-active forms as exhibited by the α-H195Q variant of Azotobacter vinelandii nitrogenase MoFe protein. The hi(5)-CO EPR signal converted to the hi-CO EPR signal, which reverted at 10 K. FT-IR monitoring revealed an exquisitely light-sensitive "Hi-2" species with bands at 1932 and 1866 cm-1 that yielded "Hi-1" with bands at 1969 and 1692 cm-1, which reverted to "Hi-2". The similarities of photochemical behavior and recombination kinetics showed, for the first time, that hi-CO EPR and "Hi-1" IR signals arise from one chemical species. hi(5)-CO EPR and "Hi-2" IR signals are from a second species, and lo-CO EPR and "Lo-2" IR signals, formed after prolonged illumination, are from a third species. Comparing FT-IR data with CO-inhibited MoFe-protein crystal structures allowed assignment of CO-bonding geometries in these species.

Catalytic reductive ring opening of epoxides enabled by zirconocene and photoredox catalysis

Catalytic reductive ring opening of epoxides enabled by zirconocene and photoredox catalysis

High-efficient carbazole-based photo-bleachable dyes as free radical initiators for visible light polymerization

The development of dyes with both high initiating efficiency and photobleaching properties is of importance for the photopolymerization of thick materials and still an emerging challenge. Carbazole-based photo-bleachable dyes CMs (CM-1 and CM-2) and CIs (CI-1 and CI-2) as free radical initiators for visible light polymerization were designed and synthesized. Their structures were confirmed by 1H NMR, 13C NMR, and HR-MS. Through electron paramagnetic resonance (EPR) analysis and visible light photolysis experiments, the free radical generation mechanisms of CMs and CIs were proposed. CMs and CIs could effectively initiate the photopolymerization of 1, 6-hexanediol diacrylate (HDDA) under LED@455 nm exposure. Among these dyes, CM-2 and CI-2 with carboxylic acid in their structures showed better free radical initiating efficiencies and lower extraction rates. In addition, at a concentration of 2 × 10−5 mol/L, CM-2/MDEA exhibited the better photopolymerization rates and double bond conversions in comparison to CQ/MDEA systems. Under the irradiation of visible light, in particular, dyes CM-2 and CI-2 could successfully initiate the polymerization of thick films of 12–13 mm to form colorless polymers. Thus, these carbazole-based photo-bleachable dyes have great potential in deep photocuring for the preparation of thick materials.

Norcaradiene Synthesis via Visible-Light-Mediated Cyclopropanation Reactions of Arenes.

Cyclopropanation reactions of carbenes with arenes provide a straightforward pathway to norcaradienes or cycloheptatrienes. This reaction normally requires harsh reaction conditions or transition-metal catalysts. In this report, we describe the metal-free visible-light photolysis of aryl diazoacetates in aromatic solvents, which provides access to the norcaradiene ring system in a highly regio- and stereoselective manner. The mild reaction conditions of this approach also allow chemoselective cyclopropanation of substituted arenes without competing C-H functionalization reactions.

Catalyst-Free [2,3]-Sigmatropic Rearrangement Reactions of Photochemically Generated Ammonium Ylides

The rearrangement reaction of ammonium ylides furnishes valuable α,α-disubstituted amino esters. In this work, we describe the visible-light photolysis reaction of aryldiazoacetates in the presence of tertiary amines that react via a free ammonium ylide in a sigmatropic rearrangement reaction to provide amino esters in moderate to very good yields (33 examples, up to 97% yield).

Visible Light Induced Metal-Free Carbene N-Carbazolation.

Metal-free N–H functionalization reactions represent an important strategy for sustainable C–N coupling reactions. In this report, we describe the visible light photolysis of aryl diazoacetates in the presence of some N-heterocycles that enables mild, metal-free N–H functionalization reactions of carbazole and azepine heterocycles (15 examples, up to 83% yield).

Mechanism of Visible-Light Photooxidative Demethylation of Toluidine Blue O

Experiments and theoretical calculations by density functional theory (DFT) have been carried out to examine a self-sensitized type I photooxidation of toluidine blue O (TBO+). This study attempts to build a connection between visible-light photolysis and demethylation processes of methylamine compounds, such as TBO+. We show that controlled photoinduced mono- and double-demethylation of TBO+ can be achieved. The kinetics for the appearance rate of the mono-demethylated TBO+ and the double-demethylated TBO+ were found to fit pseudo-first-order kinetics. DFT calculations have been used to examine the demethylation of TBO+ and included N, N-dimethylaniline as a model compound for TBO+. The results show an oxygen-dependent demethylation process. The mechanism for the sequential methyl loss is proposed to be due to H• or e-/H+ transfer to 3TBO+* followed by a reaction of TBO+• with O2, yielding a C-peroxyTBO+• intermediate. Instead of aminyl radical peroxyl formation, i.e., N-peroxyTBO+•, the C-centered peroxyTBO+• is favored, that upon dimerization (Russell mechanism) leads to dissociation of formaldehyde from the methylamine site.

Silicone-Thioxanthone: A Multifunctionalized Visible Light Photoinitiator with an Ability to Modify the Cured Polymers.

A silicone-thioxanthone (STX) visible light photoinitiator was prepared by the nucleophilic substitution reaction of 2-[(4-hydroxybenzyl)-(methyl)-amino]-9H-thioxanthen-9-one (TX-HB) and γ-chloropropylmethylpolysiloxane-co-dimethyl-polysiloxane (PSO-Cl). Its structure was confirmed by 1H NMR, 13C NMR, FTIR, UV-vis and GPC. The photopolymerization kinetics of 1, 6-Hexanedioldiacrylate (HDDA) and trimethylolpropane triacrylate (TMPTA) initiated by STX confirmed that STX is an efficient photoinitiator. Its visible light photolysis experiment and the photopolymerization kinetics studies implied that a possible synergistic effect existed between two adjacent thioxanthone groups. Moreover, a higher migration stability was revealed in STX than 2-benzyl (methyl) amino-9H-thioxanthen-9-one (TX-B). STX could change the surface property of the cured film of polyurethane diacrylate prepolymer (PUA) from hydrophilic to hydrophobic, as well as change the thermal stability of the polymer network. Meanwhile, it could improve the resistance against water and acid. Thus, STX is an effective multifunctionalized photoinitiator.

Designing Photolabile Ruthenium Polypyridyl Crosslinkers for Hydrogel Formation and Multiplexed, Visible-light Degradation.

Photoresponsive materials afford spatiotemporal control over desirable physical, chemical and biological properties. For advanced applications, there is need for molecular phototriggers that are readily incorporated within larger structures, and spatially-sequentially addressable with different wavelengths of visible light, enabling multiplexing. Here we describe spectrally tunable (λmax = 420–530 nm) ruthenium polypyridyl complexes functionalized with two photolabile nitrile ligands that present terminal alkynes for subsequent crosslinking reactions, including hydrogel formation. Two Ru crosslinkers were incorporated within a PEG–hydrogel matrix, and sequentially degraded by irradiation with 592 nm and 410 nm light.

Photochemical Water Oxidation in a Buffered Tris(2,2'-bipyridyl)ruthenium-Persulfate System Using Iron(III)-Modified Potassium Manganese Oxides as Catalysts.

Study of manganese oxides for electrocatalytic and photocatalytic oxidation of water is an active area of research. The starting material in this study is a high-surface-area disordered birnessite-like material with K+ in the interlayers (KMnOx). Upon ion-exchange with Fe3+, the disordered layer structure collapses (Fe(IE)MnOx), and the surface area is slightly increased. Structural analysis of the Fe(IE)MnOx included examination of its morphology, crystal structure, vibrational spectra, and manganese oxidation states. Using the Ru(bpy)32+–persulfate system, the dissolved and headspace oxygen upon visible light photolysis with highly dispersed Fe(IE)MnOx was measured. The photocatalytic activity for O2 evolution of the Fe(IE)MnOx was three times better than KMnOx, with the highest rate being 9.3 mmolO2 molMn–1 s–1. The improvement of the photocatalytic activity was proposed to arise from the increased disorder and interaction of Fe3+ with the MnO6 octahedra. As a benchmark, colloidal IrO2 was a better photocatalyst by a factor of ∼75 over Fe(IE)MnOx.

Photolytic Reactivity of Organometallic Chromium Bipyridine Complexes.

Known stable [Cr(bpy)2(Ph)2](BPh4) complexes undergo reductive elimination of biphenyl with visible-light photolysis using household incandescent or compact fluorescent light bulbs. A series of [Cr(R-bpy)2(Ar)2](X) complexes (R = H or CMe3; Ar = Ph, C6H4-CMe3, or C6H4-OMe; X = I, BPh4, or PF6) were prepared, and the effect of varying the bipyridine and aryl ligands on the UV-visible spectra and electrochemistry of the chromium(III) complexes was investigated. Photolysis of a mixture of two different bis(aryl) complexes gave only the homocoupled biaryl products by 1H NMR and gas chromatography/mass spectrometry analysis. The initial product of photoinduced reductive elimination of [Cr(bpy)2(Ar)2](PF6) was trapped with bipyridine to generate [Cr(bpy)3](PF6) and with benzoyl peroxide to form [Cr(bpy)2(O2CPh)2](PF6). The latter chromium(III) bis(benzoate) complex was also synthesized by the addition of bipyridine and PhCO2H to Cp2Cr, followed by air oxidation. The neutral Cr(bpy)(S2CNMe2)Ph2 complex also generated biphenyl upon visible-light photolysis. While the treatment of Cr(tBu-bpy)(dpm)Cl2 [dpm = (OCtBu)2CH] with AgO2CPh gave trans-Cr(tBu-bpy)(dpm)(O2CPh)2, reaction of the dichloro precursor with PhMgCl produced anionic [Cr(tBu-bpy)Ph3]- with [Mg(dpm)(THF)4]+ as the countercation, with both complexes characterized by single-crystal X-ray diffraction. Protonolysis of Cr(bpy)Ph3(THF) with 8-hydroxyquinoline produced Cr(bpy)(quin)Ph2, which generated biphenyl under visible-light photolysis, and the initial product of reductive elimination was trapped by bipyridine or benzoyl peroxide. A related Cr(bpy)(quin)2 complex was synthesized by protonolysis of Cr(bpy)[N(SiMe3)2]2 and characterized by single-crystal X-ray diffraction.

Visible-light photolysis of corrole-manganese(IV) nitrites to generate corrole-manganese(V)-oxo complexes

Photolysis of highly photo-labile corrole-manganese(IV) nitrites by visible light was studied in three corrole systems with different electronic environments. As observed in all three systems, homolytic cleavage of ON bond of nitrite ligand resulted in one-electron photo-oxidation to generate manganese(V)-oxo corroles, as determined by their distinct UV–vis spectra and kinetic behaviors. The spectral and kinetic results are rationalized by a multiple oxidation model, where the electron-demand MnV-oxo species may serve as direct two-electron oxidant for oxygen atom transfer reactions and less electron-demand systems undergo a disproportionation reaction to form a putative manganese(VI)-oxo corrole as the true oxidant.

An investigation of ligand effects on the visible light-induced formation of porphyrin–iron(iv)-oxo intermediates

Depending on the structure of the porphyrin ligands, the visible light photolysis of porphyrin–iron(iii) bromates produced iron(iv)-oxo radical cations or iron(iv)-oxo porphyrins, permitting direct kinetic studies of their oxidation reactions.

Photochemical generation of manganese(IV)-oxo porphyrins by visible light photolysis of dimanganese(III) μ-oxo bis-porphyrins

Visible light photolysis of dimanganese(III) μ-oxo bis-porphyrins, [MnIII(Por)]2O, was studied in three porphyrin systems with different electronic structures. Direct conversion of manganese (III) μ-oxo dimers to manganese(IV)-oxo porphyrins plus manganese(III) products has been observed in benzene solution upon light irradiation. The spectral signature of MnIV(Por)(O) was further confirmed by production of the same species in the known experiment of the MnIII(Por)Cl with PhI(OAc)2. Continuous irradiation of dimanganese(III) μ-oxo bis-porphyrins in the presence of pyridine or triphenylphosphine gave rise to the formation of MnII(Por)(Py) or MnII(Por)(PPh3) which were stable to be detected. A photo-disproportionation mechanism similar to that for diiron(III) μ-oxo bis-porphyrins was proposed to explain above photochemical behaviors of the three dimanganese(III) μ-oxo bis-porphyrins.

A new approach to polycyclic azaarenes: visible-light photolysis of vinyl azides in the synthesis of diazabenzopyrene and diazaperylene

The Hemetsberger indole synthesis was repurposed for the preparation of luminescent electron-deficient azaarenes which display dual-mode pH fluorescence sensing properties.

Wavelength-dependent isotope fractionation in visible light O3 photolysis and atmospheric implications

The 17O and 18O isotope fractionation associated with photolysis of O3 in the Chappuis band was determined using a broadband light source with cutoff filters at 455, 550, and 620 nm and narrowband light sources at 530, 617, and 660 nm. The isotope effects follow a mass-dependent fractionation pattern (δ17O/δ18O = 0.53). Contrary to theoretical predictions, fractionations are negative for all wavelength ranges investigated and do not change signs at the absorption cross-section maximum. Our measurements differ from theoretical calculations by as much as 34‰ in inline image = (18J/16J − 1). The wavelength dependence is also weaker than predicted. Photo-induced fractionation is strongest when using a low-wavelength cutoff at 620 nm with inline image = −26.9(±1.4)‰. With decreasing wavelength, fractionation values diminish to inline image = −12.9(±1.3)‰ at 530 nm. Results from an atmospheric model demonstrate that visible light photolysis is the most important tropospheric sink of O3, which thus contributes about one sixth to the ozone enrichment.