Quantum Yield Of Photoreduction Research Articles

Accelerating Surface Photoreactions Using MoS2-FeS2 Nanoadsorbents: Photoreduction of Cr(VI) to Cr(III) and Photodegradation of Methylene Blue.

Nanocubic MoS2-FeS2, as a photocatalyst, was synthesized with high catalytic active edges and high specific surface areas with the capability of absorbing visible light. The results showed that the photocatalytic efficiency of nanocubic MoS2-FeS2 for adsorption/degradation of methylene blue (MB) as well as the reduction of Cr(VI) was high. The adsorption process was found to follow a kinetic model of a pseudo-second-order kind (Qe.cal = 464 mg g-1) along with an isotherm described by the Langmuir model with Qe.cal = 340 mg g-1. The photodegradation process was achieved by holes. It was found that the photodegradation rate constant of MB by MoS2-FeS2 (0.203 min-1) was about 22 times higher than that of MoS2 (0.0091 min-1). The percent apparent quantum yield for photoreduction of Cr(VI) to Cr(III) using MoS2-FeS2 (5.7%) was about 33 times higher than utilizing MoS2 (0.1709%). Therefore, the synergistically prolonged visible-light harvesting as well as the photocarrier diffusion length proved that MoS2-FeS2 nanotubes can effectively be utilized in environmental pollutant's remediation.

Photoreductive dissolution of cerium oxide nanoparticles and their size-dependent absorption properties.

Cerium oxide has attracted attention recently for its photocatalytic properties, but there are gaps in understanding its performance, especially at low and high pH. UV irradiation of ceria nanoparticles causes electrons from photogenerated electron-hole pairs to localize as small polarons, yielding Ce3+ ions. In pH 10 solution, ceria nanoparticles capped with polyacrylic acid ligands can accumulate large numbers of Ce3+ defects as revealed by strong bleaching of the absorption onset. In contrast, we show that UV irradiation of several-nanometer diameter ceria nanoparticles in acidic (pH < 3) aqueous solution releases Ce3+ ions into solution with a quantum yield that approaches 70% and that varies with excitation wavelength, particle size, and the presence of a hole scavenger (glycerol) on the nanoparticle surface. The instability of Ce3+ at the nanoparticle surface and the ability of electron small polarons to migrate to the surface by hopping strongly suggest that nanoceria is fully oxidized and essentially free of Ce3+ centers at pH < 3. Efficient photoreduction and the excellent stability of unirradiated nanoparticles make it easy to shrink the nanoparticles using only light, while maintaining them in a fully oxidized state. This enables study of the size-dependent absorption properties of ceria nanoparticles that are free of Ce3+ defects. No evidence of quantum confinement is observed, consistent with highly localized excited states. The observed quantum yields of photoreduction are higher than reported for other metal oxides, revealing that a significant fraction of electron-hole pairs are available for driving surface redox reactions, even in fully oxidized particles.

Chemical and structural analysis of a photoactive vertebrate cryptochrome from pigeon

Computational and biochemical studies implicate the blue-light sensor cryptochrome (CRY) as an endogenous light-dependent magnetosensor enabling migratory birds to navigate using the Earth's magnetic field. Validation of such a mechanism has been hampered by the absence of structures of vertebrate CRYs that have functional photochemistry. Here we present crystal structures of Columba livia (pigeon) CRY4 that reveal evolutionarily conserved modifications to a sequence of Trp residues (Trp-triad) required for CRY photoreduction. In ClCRY4, the Trp-triad chain is extended to include a fourth Trp (W369) and a Tyr (Y319) residue at the protein surface that imparts an unusually high quantum yield of photoreduction. These results are consistent with observations of night migratory behavior in animals at low light levels and could have implications for photochemical pathways allowing magnetosensing.

Ultrafast Photoinduced Interfacial Proton Coupled Electron Transfer from CdSe Quantum Dots to 4,4'-Bipyridine.

Pyridine and derivatives have been reported as efficient and selective catalysts for the electrochemical and photoelectrochemical reduction of CO2 to methanol. Although the catalytic mechanism remains a subject of considerable recent debate, most proposed models involve interfacial proton coupled electron transfer (PCET) to electrode-bound catalysts. We report a combined experimental and theoretical study of the photoreduction of 4,4'-bipyridium (bPYD) using CdSe quantum dots (QDs) as a model system for interfacial PCET. We observed ultrafast photoinduced PCET from CdSe QDs to form doubly protonated [bPYDH2](+•) radical cations at low pH (4-6). Through studies of the dependence of PCET rate on isotopic substitution, pH and bPYD concentration, the radical formation mechanism was identified to be a sequential interfacial electron and proton transfer (ET/PT) process with a rate-limiting pH independent electron transfer rate constant, kint, of 1.05 ± 0.13 × 10(10) s(-1) between a QD and an adsorbed singly protonated [bPYDH](+). Theoretical studies of the adsorption of [bPYDH](+) and methylviologen on QD surfaces revealed important effects of hydrogen bonding with the capping ligand (3-mercaptopropionic acid) on binding geometry and interfacial PCET. In the presence of sacrificial electron donors, this system was shown to be capable of generating [bPYDH2](+•) radical cations under continuous illumination at 405 nm with a steady-state photoreduction quantum yield of 1.1 ± 0.1% at pH 4. The mechanism of bPYD photoreduction reported in this work may provide useful insights into the catalytic roles of pyridine and pyridine derivatives in the electrochemical and photoelectrochemical reduction of CO2.

Enhancing photo-reduction quantum efficiency using quasi-type II core/shell quantum dots.

Quantum confined semiconductor nanocrystals have emerged as a new class of materials for light harvesting and charge separation applications due to the ability to control their properties through rational design of their size, shape and composition. We report here a study of enhancing the quantum yield of methyl viologen (MV2+) photoreduction using colloidal quasi-type II CdSe/CdS core/shell quantum dots (QDs). The steady-state quantum yield of MV+˙ radical generation, in the presence of thiols as sacrificial donors, increased monotonically with the CdS shell thickness within the studied thickness regime (0-4.7 CdS monolayers). Using ultrafast transient absorption and time-resolved photoluminescence decay spectroscopy, we found that both the rates of electron transfer from the QD to MV2+ and the subsequent charge recombination in QD+-MV+˙ complexes decreased exponentially with the shell thickness, consistent with calculated 1S electron and hole densities at the QD surfaces, respectively. Interestingly, the hole transfer rate remained relatively independent of shell thickness, likely due to a cancellation of the reduction of hole transfer coupling strength with the increased number of hole acceptor ligands on the QD surface at larger shell thickness. As a result, with increasing CdS shell thickness, the charge recombination loss decreases, enhancing the photoreduction quantum efficiency. This novel approach for improving photoreduction quantum efficiency should be applicable to many type II and quasi-type II core/shell quantum dots.

Wavelength-dependent photooxidation and photoreduction of protochlorophyllide and protochlorophyll in the innermost leaves of cabbage (Brassica oleracea var. capitata L.).

The photoreduction and photooxidation processes of different protochlorophyll(ide) forms were studied in the innermost leaves of cabbage (Brassica oleracea var. capitata L.) under monochromatic irradiations. Room-temperature fluorescence emission spectra were measured from the same leaf spots before and after illumination to follow the wavelength dependence of the photochemical reactions. Short-wavelength light of 7 µmol photons m(-2) s(-1) (625-630 nm) provoked mainly bleaching, and longer wavelengths (630-640 nm) caused both bleaching and photoreduction, while above 640 nm resulted in basically photoreduction. When bleached leaves were kept in darkness at room temperature, all protochlorophyll(ide) forms regenerated during 72 h. Oxygen-reduced environment decreased the extent of bleaching suggesting the involvement of reactive oxygen species. These results confirm that the short-wavelength, 628 nm absorbing, and 633 nm emitting protochlorophyll(ide) form in etiolated cabbage leaves sensibilizes photooxidation. However, the 628 nm light at low intensities stimulates the photoreduction of the longer wavelength protochlorophyllide forms. Kinetic measurements showed that photoreduction saturates at a low PFD (photon flux density) compared to bleaching, suggesting that the quantum yield of photoreduction is higher than that of bleaching.

ChemInform Abstract: Sunlight‐Driven Copper‐Catalyst Activation Applied to Photolatent Click Chemistry.

AbstractThe copper‐catalyst CUA can be activated by irradiation with daylight or light of 365 nm.

Ultrafast Exciton Dynamics and Light-Driven H2 Evolution in Colloidal Semiconductor Nanorods and Pt-Tipped Nanorods

Colloidal quantum confined one-dimensional (1D) semiconductor nanorods (NRs) and related semiconductor-metal heterostructures are promising new materials for efficient solar-to-fuel conversion because of their unique physical and chemical properties. NRs can simultaneously exhibit quantum confinement effects in the radial direction and bulk like carrier transport in the axial direction. The former implies that concepts well-established in zero-dimensional quantum dots, such as size-tunable energetics and wave function engineering through band alignment in heterostructures, can also be applied to NRs; while the latter endows NRs with fast carrier transport to achieve long distance charge separation. Selective growth of catalytic metallic nanoparticles, such as Pt, at the tips of NRs provides convenient routes to multicomponent heterostructures with photocatalytic capabilities and controllable charge separation distances. The design and optimization of such materials for efficient solar-to-fuel conversion require the understanding of exciton and charge carrier dynamics. In this Account, we summarize our recent studies of ultrafast charge separation and recombination kinetics and their effects on steady-state photocatalytic efficiencies of colloidal CdS and CdSe/CdS NRs and related NR-Pt heterostructures. After a brief introduction of their electronic structure, we discuss exciton dynamics of CdS NRs. By transient absorption and time-resolved photoluminescence decay, it is shown that although the conduction band electrons are long-lived, photogenerated holes in CdS NRs are trapped on an ultrafast time scale (∼0.7 ps), which forms localized excitons due to strong Coulomb interaction in 1D NRs. In quasi-type II CdSe/CdS dot-in-rod NRs, a large valence band offset drives the ultrafast localization of holes to the CdSe core, and the competition between this process and ultrafast hole trapping on a CdS rod leads to three types of exciton species with distinct spatial distributions. The effect of the exciton dynamics on photoreduction reactions is illustrated using methyl viologen (MV(2+)) as a model electron acceptor. The steady-state MV(2+) photoreduction quantum yield of CdSe/CdS dot-in-rod NRs approaches unity under rod excitation, much larger than CdSe QDs and CdSe/CdS core/shell QDs. Detailed time-resolved studies show that in quasi-type II CdSe/CdS NRs and type II ZnSe/CdS NRs strong quantum confinement in the radial direction facilitates fast electron transfer and hole removal, whereas the fast carrier mobility along the axial direction enables long distance charge separation and slow charge recombination, which is essential for efficient MV(2+) photoreduction. The NR/MV(2+) relay system can be coupled to Pt nanoparticles in solution for light-driven H2 generation. Alternatively, Pt-tipped CdS and CdSe/CdS NRs provide fully integrated all inorganic systems for light-driven H2 generation. In CdS-Pt and CdSe/CdS-Pt hetero-NRs, ultrafast hole trapping on the CdS rod surface or in CdSe core enables efficient electron transfer from NRs to Pt tips by suppressing hole and energy transfer. It is shown that the quantum yields of photodriven H2 generation using these heterostructures correlate well with measured hole transfer rates from NRs to sacrificial donors, revealing that hole removal is the key efficiency-limiting step. These findings provide important insights for designing more efficient quantum confined NR and NR-Pt based systems for solar-to-fuel conversion.

Photochemistry of copper(II) chlorocomplexes in acetonitrile: Trapping the ligand-to-metal charge transfer excited state relaxations pathways

Photochemistry of [Cu(MeCN)3Cl]+, [Cu(MeCN)Cl3]−, and [CuCl4]2− copper(II) chlorocomplexes in acetonitrile solution is studied by means of the combination of the steady-state photolysis and ultrafast transient absorption methods. The main relaxation pathways of the initially excited ligand-to-metal charge transfer states are internal conversion to the ground state, ionic dissociation without (photo)reduction of copper(II), and radical dissociation with (photo)reduction of copper(II). The copper(II)-to-copper(I) photoreduction quantum yields obtained from steady-state photolysis correlate with ultrafast spectroscopy data. The presence of oxygen does not affect the photoreduction quantum yields, which do not exceed 7% for the complexes studied and decrease in the series: [Cu(MeCN)3Cl]+>[Cu(MeCN)Cl3]−>[CuCl4]2−.

Sunlight-driven copper-catalyst activation applied to photolatent click chemistry.

The synthesis, full characterization, photoreduction properties, and catalytic activity for the copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction of a copper(II)-DMEDA (N,N'-dimethylethylendiamine) complex is reported. Spectroscopic studies (UV/Vis, EPR) demonstrated that under daylight illumination highly effective copper(II) to copper(I) reduction occurs in this complex. These findings are in agreement with a high photoreduction quantum yield value of 0.22 in MeOH, and a value approaching unity as determined in THF. The reduction process, which can also be conducted by irradiation at 365 nm by using a standard TLC (thin layer chromatography) lamp, is ascribed to a highly efficient photoinduced electron transfer (PET) process mediated by the benzophenone photosensitizer present in the carboxylate counterion. Having deaerated the reaction mixture, the photogenerated copper(I) species proved to be highly active for the CuAAC reaction, demonstrated by reactions conducted with low catalyst loading (0.5 mol %) on a range of clickable protected and non-protected mono- and disaccharides. Once initiated, the reaction can be stopped at any time on introducing air into the reaction medium. Deoxygenation followed by irradiation restores the activity, making the copper(II)-DMEDA complex a switchable catalyst of practical value.

Synthesis, Spectral Characterization, and Solvent Effects on the Electro- and Photo-Reduction of Co(III) Complexes

Six new Co(III) complexes of the type cis-β-[Co(dmen)2(4-R-Py)Cl]Cl2 (where dmen = NN′-dimethylethylenediamine, R = H, Me, Et, t-Bu, COMe, and CN) have been synthesized and characterized by elemental analysis, UV-Vis, FT-IR, 1H NMR, TGA, and differential pulse voltammetric (DPV) techniques. Further, the effect of solvent and structure on the electro- and photo- reduction of these Co(III) complexes have been studied in propan-2-ol/water and 1,4-dioxane/water binary mixtures. The redox potential (E1/2) and the photo-reduction quantum yield (ΦCo(II)) data were correlated with solvent and structural parameters with an aim to shed some light on the mechanism of these reactions. Correlation of E1/2 and ΦCo(II) with solvent parameters indicated that the reactivity is influenced largely by dipolarity/polarizability of the medium.

Solvent H-bonding and structural effects on the photo-reduction of Co(III) complexes in water/propan-2-ol and water/1,4-dioxane media

The photo-reduction of a series of cobalt(III) complexes of the type cis-β-[Co(trien)(4-R-Py)Cl]Cl 2 where trien=triethylenetetraamine and R = H, Me, Et, t-Bu, COMe, and CN has been studied in water/propan-2-ol and water/1,4-dioxane media of varying compositions. The photo-reduction quantum yield (Φ Co(II)) data were correlated with solvent and structural parameters with an aim to shed some light on the mechanism of the reaction. Correlation of Φ Co(II) with macroscopic solvent parameters viz. relative permittivity indicates that the reactivity is influenced by both specific and non-specific solute–solvent interactions. Kamlet–Taft solvatochromic comparison method was used to separate and quantify these effects. The observed non-linear concave downwards type Hammett plot is explained by assuming shift in the excited state within the same overall reaction pathway.

Solvent and structural effects on the photo-reduction of cobalt(III) complexes in aquo-organic solvent media possessing different H-bonding properties

The photo-reduction of a series of cobalt(III) complexes of the type cis-β-[Co(ampy) 2 (4-R-Py)Cl]Cl 2 where ampy = 2-aminomethylpyridine and R = H, Me, Et, t-Bu, COMe, and CN has been studied in propan-2-ol/water and 1,4-dioxane/water medium. The photo-reduction quantum yield (Φ Co II ) data were correlated with solvent and structural parameters with an aim to shed some light on the mechanism of these reactions. Increase in the percentage of organic co-solvent in both the medium increased the photo-reduction quantum yield. Correlation of Φ Co II with macroscopic solvent parameters viz. relative permittivity indicated that the reactivity is influenced by both specific and non-specific solute-solvent interactions. Kamlet-Taft solvatochromic comparison method was used to separate and quantify these effects. H-bonding property of the mixture was found to dominate the solvation and consequently the magnitude of the quantum yield.

Solvent and structural effects on the electro- and photo-reduction of cis - β -Co(trien)(RC6H4NH2)Cl]Cl2 type complexes in water/1,4-dioxane media

The electro- and photo-reduction of a series of cobalt(III) complexes of the type cis-β-[Co(trien)(RC6H4NH2)Cl]Cl2 where R=H, p-OMe, p-OEt, p-Me, p-Et, p-F and m-Me has been studied in 1,4-dioxane/water. The redox potential (E 1/2) and photo-reduction quantum yield (φCo(II)) data were correlated with solvent and structural parameters to shed light on the mechanism of these reactions. Correlation of E 1/2 and φCo(II) with macroscopic solvent parameters viz. relative permittivity indicates that the reactivity is influenced by both specific and non-specific solute-solvent interactions. The Kamlet-Taft solvatochromic comparison method was used to separate and quantify these effects. Increasing the percentage of organic co-solvent in the medium enhances both reduction processes; there exists good correlation between E 1/2 and φCo(II) suggesting a similar solvation in these redox processes.

Correlation Analysis of Reactivity in the Photo- and Electro-Reduction of Cobalt(III) Complexes in Binary Organic Solvent/Water Mixtures

The photo- and electro-reduction of a series of cobalt(III) complexes of the type cis-β - [Co(trien)(RC6H4NH2)Cl]Cl2 with R = H, p-OMe, p-OEt, p-Me, p-Et, p-F, and m-Me has been studied in binary propan-2-ol/water mixtures. The redox potential (E1/2) and photo-reduction quantum yield (ΦCo(II)) data were correlated with solvent and structural parameters with the aim to shed some light on the mechanism of these reactions. The correlation of E1/2 and ΦCo(II) with macroscopic solvent parameters, viz. relative permittivity, indicated that the reactivity is influenced by both specific and non-specific solute-solvent interactions. The Kamlet-Taft solvatochromic comparison method was used to separate and quantify these effects: An increase in the percentage of organic cosolvent in the medium enhances both reduction processes, and there exists a good linear correlation between E1/2 and ΦCo(II), suggesting a similar solvation of the participants in these redox processes.

Photocatalytic Reduction of NO by CO on Titanium Dioxide under Visible Light Irradiation

It is shown for the first time that the photoassisted reduction of NO by CO into N2 and N2O can occur on TiO2 catalysts upon visible light irradiation (λ > 380 nm) at room temperature. The selectivity of photoreduction of NO into N2 reaches 90−95%. The CO2 formed which predominantly remains on the surface can be quantitatively desorbed after completion of the photoreaction by heating TiO2 to ∼500 K. The rates of NO consumption and product accumulation remain virtually constant upon successive admissions of the CO−NO mixture thus indicating a high stability of catalyst activity. It is found that the quantum yield of NO photoreduction by CO is considerably greater for visible light irradiation (λ = 405 + 436 nm) than for UV irradiation (λ = 365 nm). Experiments with 18O-enriched NO revealed that, under visible light irradiation, an intense oxygen isotopic exchange between NO and TiO2 develops. The photocatalytic reaction requires the presence in nonstoichiometric TiO2-x of electron-donor centers (Ti3+ ions, F and F+ centers) able to absorb visible light. A reaction mechanism is proposed which includes the following stages: (a) NO photoadsorption along two parallel routes, by e- capture from the electron-donor center by NO to yield adsorbed NO- species and by NO interaction with the hole O- to give adsorbed nitrite NO2-; (b) reduction of NO- into N2O and further into N2; and (c) photoreduction of adsorbed nitrite NO2- into N2O and further into N2 by CO which regenerates the donor centers. It is assumed that the photoinduced oxygen heteroexchange proceeds via adsorbed nitrite complexes.

Sensitization of photo-reduction of the polyoxometalate anions [S2M18O62]4? (M = Mo, W) in the visible spectral region by the [Ru(bpy)3]2+ cation

Voltammetric, photo-physical and photo-electrochemical properties of the Dawson polyoxometalate anions alpha-[S(2)M(18)O(62)](4-) (M = Mo, W) are presented, both in the presence and absence of a series of [Ru(II)L(n)](+/2+) cations [L(n) = (bpy)(3), (bpy)(2)(Im)(2), (bpy)(2)(dpq), (bpy)(2)(box) and (biq)(2)(box)]. Electrochemical processes for both the anion and Ru(II/III) couples were detected in solutions of the salts [Ru(II)L(n)](2)[S(2)M(18)O(62)] in dimethylformamide (0.1 M Bu(4)NPF(6)) by both cyclic and hydrodynamic voltammetries. Responses were also detected when the solid salts were adhered to the surface of a glassy carbon electrode in contact with an electrolyte in which they are insoluble (CH(3)CN; 0.1M Bu(4)NPF(6)). Photolysis experiments were performed on solutions of the salts [R(4)N](4)[S(2)M(18)O(62)] (R = n-butyl or n-hexyl) and [Ru(II)L(n)](2)[S(2)M(18)O(62)] at 355 and 420 nm in dimethylformamide and acetonitrile in the presence and absence of benzyl alcohol (10% v/v). When associated with [Ru(bpy)(3)](2+), the molybdate anion exhibited a large increase in the quantum yield for photo-reduction at 420 nm. The quantum yield for the tungstate analogue was lower but the experiments again provided clear evidence for sensitization of the photo-reduction reaction in the visible spectral region. The origin of this sensitization is ascribed to the new optical transition observed around 480 nm in static ion clusters {[Ru(bpy)(3)][S(2)M(18)O(62)]}(2-) and {[Ru(bpy)(3)](2)[S(2)M(18)O(62)]} present in solution. Measurable photocurrents resulted from irradiation of solutions of the anions with white light in the presence of the electron donor dimethylformamide. Evidence is also presented for possible quencher-fluorophore interactions in the presence of certain [Ru(II)L(n)](+) cations.

Chain Mechanism in the Photocleavage of Phenacyl and Pyridacyl Esters in the Presence of Hydrogen Donors

[reaction: see text] Excited phenacyl and 3-pyridacyl esters of benzoic acid react with an excess of aliphatic alcohols in a chain reaction process involving hydrogen transfer from the ketyl radical intermediates, leading to benzoic acid in addition to acetophenone and 3-acetylpyridine, respectively, as the byproducts. While the maximum quantum yields reached 4 in both cases, the 2- or 4-pyridacyl ester photoreduction proceeded with the efficiency below 100% under the same conditions. The investigation indicates that a radical coupling between ketyl radicals, both formed from the excited ester by hydrogen abstraction from an alcohol, is accompanied by the elimination of benzoic acid from the ester ketyl radical itself. A partitioning between two reactions was found to be remarkably sensitive to the chromophore nature, such as a position of the nitrogen atom in the pyridacyl moiety. The magnitude of a radical chain process is dependent on the efficiency of consecutive steps that produce free radicals capable of a subsequent ester reduction. The driving force of a possible electron transfer from the ketyl radicals to the ester has been excluded on the basis of cyclic voltametry measurements. The observed quantum yields of photoreduction were found to be diminished by formation of relatively long-lived light absorbing transients, coproducts obtained apparently by secondary photochemical reactions. Additionally, it is shown that basic additives such as pyridine can further increase the efficiency of the photoreduction by a factor of 4. A radical nature of the reduction mechanism was supported by finding a large kinetic chain length of an analogous reaction initiated by free radicals generated thermally yet again when phenacyl or 3-pyridacyl benzoate was used. Both phenacyl and pyridacyl chromophores are pronounced to be valuable as the photoremovable protecting groups when high quantum and chemical yields of carboxylic acid elimination are important, but higher concentrations of the hydrogen atom donors are not destructive for a reaction system or are experimentally impractical.

Kinetics of photoreduction of 9,10-phenanthrenequinone in the presence of amines and polymethylbenzenes

A study of the kinetics of photoreduction of 9,10-phenanthrenequinone in the presence of hydrogen donors (para-substituted N,N-dimethylanilines and polymethylbenzenes) showed that plots of the quantum yield of photoreduction (ϕH) and apparent reaction rate constant (kH) vs. oxidation potential of hydrogen donors are extreme. In the presence of amines, kH and ϕH increase, as a whole, whereas they decrease in the presence of polymethylbenzenes. In coordinates ϕH-ΔGe (ΔGe is the change in the free energy of electron transfer) for pairs quinone-H donor, ϕH increases with ΔGe approaching to zero. For the amine series, this effect is mainly in the exothermic region of ΔGe (ΔGe 0).

Photosensitization of N,N-Dimethylaniline by N,N-Dimethyl-4-nitroaniline as a New Bimolecular Photoinitiation System for Polymerization

Photophisics, photochemical and polymerization activity of N,N-dimethyl-4-nitroaniline (DMNA) alone and in the presence of N,N-dimethyl-4 (DMNA) as coinitiator were analyzed to elucidate the influence of the bifunctional character of this compound on the efficiency and mechanism of generating inititing radicals. The presence of electron donor and acceptor groups in the same moleci=ule determines the capability of DMNA to initiate the polymerozation with higher efficiency and lower initiator consumption as compared with conventional bifunctional ketones. Detailed studies of the spectroscopy of both reactants were carried out providing experimental evidence of photosensitization of DMA throught excitation energy transfer from DMNA. The consumption rate of both reactants reveals that up to 165 molecules of DMA are consumed for each DMNA molecule phoreduced in spit of the low photoreduction quantum yield of DMNA induced by DMA. The photosensitization of DMA, working concurrently to the photoreduction reaction, enhances the polymerization efficiency as compared with other nitroaromatic initiators.