Distance dependence of enhanced intersystem crossing in BODIPY-nitroxide dyads.

Photogenerated organic triplet-doublet systems have attracted an increasing amount of attention in recent years due to their versatility and suitability for a range of technological applications in the emerging field of molecular spintronics. Such systems are typically generated by enhanced intersystem crossing (EISC) preceded by photoexcitation of an organic chromophore covalently linked to a stable radical. After formation of the chromophore triplet state by EISC, triplet state and stable radical may interact, whereby the nature of the interaction depends on the exchange interaction JTR between them. If JTR surpasses all other magnetic interactions in the system, molecular quartet states may be formed by spin mixing. For the design of new spintronic materials based on photogenerated triplet-doublet systems, it is crucial to gain further knowledge about the factors influencing the EISC process and the yield of the subsequent quartet state formation. Here we investigate a series of three BODIPY-nitroxide dyads characterised by different separation distances and different relative orientations of the two spin centres. Our combined results from optical spectroscopy, transient electron paramagnetic resonance, and quantum chemical calculations suggest that the chromophore triplet formation by EISC is mediated by dipolar interactions and depends primarily on the distance between the chromophore and radical electrons, while the yield of the subsequent quartet state formation by triplet-doublet spin mixing is influenced by the absolute magnitude of JTR.

Photochemical Processes of Superbase Generation in Xanthone Carboxylic Salts.

Photobase generators are species that allow the photocatalysis of various reactions, such as thiol-Michael, thiol-isocyanate, and ring-opening polymerization reactions. However, existing compounds have complex syntheses and low quantum yields. To overcome these problems, photobase generators based on the photodecarboxylation reaction were developed. We synthesized and studied the photochemistry and photophysics of two xanthone photobase, their carboxylic acid precursors, and their photoproducts to understand the photobase generation mechanism. We determined accurate quantum yields of triplet states and photobase generation. The effect of the intermediate radical preceding the base release was demonstrated. We characterized the photophysics of the photobase by femtosecond spectroscopy and showed that the photodecarboxylation process occurred from the second excited triplet state with a rate constant of 2.2×109  s-1 .

Combined aza-Michael and radical photopolymerization reactions for enhanced mechanical properties of 3D printed shape memory polymers.

3D printed shape memory polymers (SMP) were formed by combining aza-Michael addition and light initiated radical polymerization. Amine consumption and acrylate conversion were monitored by 1H-NMR and Fourier transform infrared spectroscopies. Dynamic mechanical analysis and cyclic thermomechanical tensile tests enabled direct observation of the polymer network changes. Increased homogeneity of the 3D network and enhanced SMP properties were achieved after the reaction between residual acrylate functions trapped in the vitrified medium with the secondary amines formed during the process. This allows the fabrication of shape memory objects by 3D printing.

Photoinduced hydrosilylation through hydrogen abstraction: an NMR and computational study of the structural effect of silane.

The hydrosilylation reaction, describing the addition of Si-H bonds to unsaturated bonds, is performed in the presence of catalysts, usually highly active platinum catalysts. This work focuses on the study of a photoinduced hydrosilylation by the use of benzophenone which promotes the addition reaction of olefin on different hydrosilanes. The reactivity of silanes towards addition onto the double bond during hydrosilylation appears to depend on their structure. It was observed that the consumption of Si-H and C[double bond, length as m-dash]C functional groups increases with the irradiation time, and reaches a maximum of approx. 51% in the case of diphenylsilane. The hydrosilylation products are determined with 1H NMR, HSQC, DEPT, COSY and 13C NMR. The main product corresponds to the single adduct of the silyl radical onto the double bond. Substitution of the Si-H bond by two or three phenyls groups (triphenylsilane, diphenysilane) enhances the yield of the reaction, although diphenylsilane was found to be more efficient than triphenylsilane because of its lower steric hindrance. The ketyl radical formed after hydrogen abstraction by the triplet state of benzophenone likely forms benzopinacol, a reaction which reduces the overall yield of the hydrosilylation reaction. All these experiments are in line with DFT calculations of the Gibbs free energy of the reactions involved. This sheds new light on the photoinduced hydrosilylation process and opens the way to more active combinations of photoinitiator/silane/vinylsilane systems.

On-Demand Photopolymerization of Fiber-Reinforced Polymers Exhibiting the Shape Memory Effect.

Fiber-reinforced polymers exhibiting the shape memory effect were created on the basis of a one-pot three-step chemical process. The first step is a Michael addition, which creates linear polymer chains. The second step is free radical photopolymerization, which increases the degree of curing of polymers. The last step is post-consolidation due to the reaction of previously formed secondary amines on the residual double bonds. By employing such chemistry to impregnate glass fibers, the final composite exhibits a convincing shape memory effect, as shown by cyclic thermomechanical tests.

Analysis of Acrylic and Methacrylic Networks through Pyrolysis-GC/MS.

A direct analytical method developed to characterize UV-cured networks based on multi-step pyrolysis-gas chromatography-mass spectroscopy (GC/MS) is presented. Application of the method to characterize (meth)acrylate-based UV-cured networks is discussed. The reversion process of methacrylates is clearly observed during pyrolysis. In contrast, the decomposition of acrylates in high molecular weight degradation products is hardly detected. The potential impact of this technique to elucidate the structural and compositional nature of UV-cured polymeric networks is highlighted.

Highly reactive photothermal initiating system based on sulfonium salts for the photoinduced thermal frontal cationic polymerization of epoxides: a way to create carbon-fiber reinforced polymers.

A new combination of sulfonium salts has been investigated to cure opaque and thick carbon composite materials through photoinduced thermal frontal polymerization reaction. The photopolymerization occurs at the surface of the cycloaliphatic epoxide through the excitation of a triarylsulfonium salt and releases enough heat to decompose an alkyl-based sulfonium salt acting as a latent thermal initiator. Thus, a thermal front propagates into the medium leading to the polymerization of the whole sample. Thermal properties and optimal parameters are investigated to obtain frontal polymerization in the depth of the material. Front velocities were as high as 12.9 cm min-1 and were found to increase with an increasing concentration of thermal sulfonium salt. The effect of an addition of carbon filler is investigated with a concentration of up to 50 wt%, which allows the formation of a composite material with a high content of carbon without the need for thermal post curing.

A new synthetic pathway based on one-pot sequential aza-Michael addition and photoCuAAC click reactions.

A solvent-free process is described for the synthesis of tailor-made molecules from a one-pot, two-step approach combining aza-Michael addition and photoinduced copper(i) catalysed azide-alkyne (photo-CuAAC) reactions. After the first reaction between an amine and an acrylate, cycloaddition between an azide and an alkyne is activated by light irradiation in the presence of a copper complex. The kinetics of the aza-Michael addition and photo-CuAAC reaction were investigated by liquid state 1H NMR spectroscopy and real-time Fourier transform infrared spectroscopy. This new process represents a well-defined spatio-temporal pathway to the synthesis of bespoke intermediate molecules for various applications.

A new safranin based three-component photoinitiating system for high resolution and low shrinkage printed parts via digital light processing.

Additive manufacturing or 3D printing has attracted the interest of researchers in industry and academia because of its outstanding features. In this study, a new three-component photoinitiating system (PIS) consisting of safranin O (SFH+), thiol derivatives and diphenyl iodonium salt was used for the free radical photopolymerization of a diacrylate monomer (SR349) in DLP 3D printing. The photoinitiating characteristics of this PIS were evaluated and advantageously compared to those of a conventional PI (TPO) by using RT-FTIR. It is shown that the proposed PIS could be used as an efficient PIS for free radical photopolymerization. In addition, the resolution and shrinkage of printed parts in the presence of this three-component PIS were measured and compared to those printed using TPO as a photoinitiator. The resolution of printed parts was determined by using SEM and profilometry techniques. In addition, photorheometry was used to evaluate the linear shrinkage of samples. Moreover, the initiating mechanism of the three-component PIS was studied by using laser flash photolysis (LFP). A photocyclic mechanism was outlined for the three-component PIS which demonstrated this mechanism would be very beneficial for DLP 3D printing.

Spectroscopic Studies of the Interactions between a Cationic Cyanine Dye and a Synthetic Phyllosilicate: From Photophysics to Hybrid Materials.

The interaction of the cationic organic dye Astrazon orange R (AO-R) with the synthetic phyllosilicate Laponite leads to very interesting hybrid materials. Indeed, the Laponite nanoparticles modify the photophysical properties of AO-R, inducing a stabilization of its excited emissive state by preventing ultrafast isomerization. The long-lived emissive clay-dye hybrid complex can be used to develop efficient photoinitiating systems, leading to organic-inorganic hybrid crosslinked polymer materials.

Mechanistic Investigation of a Dual Bicyclic Photoinitiating System for Synthesis of Organic-Inorganic Hybrid Materials.

One-pot synthesis of organic-inorganic hybrid materials under light requires specific photoinitiating systems which are able to release several different initiating species after light absorption. In this paper, the reaction mechanism of a photocyclic three-component initiating system based on isopropylthioxanthone as photoinitiator and an iodonium salt and a thiol as co-initiators was studied. It is shown that this system enables simultaneous release of both radicals and protons which are able to initiate a free radical photopolymerization and the hydrolysis-condensation of a sol-gel network, respectively. Time-resolved investigations by laser flash photolysis show that the initiating species are produced within two concomitant cyclic reaction mechanisms depending on the relative quantities of the co-initiators. Protons resulting from the secondary dark reaction of the photocyclic systems are detected at the microsecond scale by means of a proton-sensitive molecular probe, and corresponding quantum yields are measured. Finally, synthesis of organic, inorganic, and hybrid materials under LED light at 395 nm is evaluated with respect to the mechanistic considerations demonstrating the dual initiating character of the system.

Versatility of Pyrylium Salt/Vinyl Ether Initiating System for Epoxide Dual-Cure Polymerization: Kick-Starting Effect of the Coinitiator.

Pyrylium salts combined with vinyl ethers are shown to act as new versatile dual-cure initiating systems for both photochemical and thermal initiation of oxirane monomers. The combination of both possibilities allows the curing of thick samples through photoinduced frontal polymerization. On the basis of quantum calculations and photochemical experiments, some clues are given about the reaction mechanisms involved. Interestingly, a sequential kick-starting effect is observed in the presence of vinyl ether enabling the curing of oxetane monomers. Thereby, this communication presents a short overview of potential of pyrylium salts in cationic polymerization of oxiranes.

Elucidation of the Key Role of [Ru(bpy)3 ](2+) in Photocatalyzed RAFT Polymerization.

Photocatalysis reactions using [Ru(II) (bpy)3 ](2+) were studied on the example of visible-light-sensitized reversible addition-fragmentation chain transfer (RAFT) polymerization. Although both photoinduced electron- and energy-transfer mechanisms are able to describe this interaction, no definitive experimental proof has been presented so far. This paper investigates the actual mechanism governing this reaction. A set of RAFT agents was selected, their redox potentials measured by cyclic voltammetry, and relaxed triplet energies calculated by quantum mechanics. Gibbs free-energy values were calculated for both electron- and energy-transfer mechanisms. Quenching rate constants were determined by laser flash photolysis. The results undoubtedly evidence the involvement of a photoinduced energy-transfer reaction. Controlled photopolymerization experiments are discussed in the light of the primary photochemical process and photodissociation ability of RAFT agent triplet states.

Photoinduced Cross-Linking of Dynamic Poly(disulfide) Films via Thiol Oxidative Coupling.

Initially developed as an elastomer with an excellent record of barrier and chemical resistance properties, poly(disulfide) has experienced a revival linked to the dynamic nature of the S-S covalent bond. A novel photobase-catalyzed oxidative polymerization of multifunctional thiols to poly(disulfide) network is reported. Based solely on air oxidation, the single-step process is triggered by the photodecarboxylation of a xanthone acetic acid liberating a strong bicyclic guanidine base. Starting with a 1 µm thick film based on trithiol poly(ethylene oxide) oligomer, the UV-mediated oxidation of thiols to disulfides occurs in a matter of minutes both selectively, i.e., without overoxidation, and quantitatively as assessed by a range of spectroscopic techniques. Thiolate formation and film thickness determine the reaction rates and yield. Spatial control of the photopolymerization serves to generate robust micropatterns, while the reductive cleavage of S-S bridges allows the recycling of 40% of the initial thiol groups.

Joint spectroscopic and theoretical investigation of cationic cyanine dye Astrazon Orange-R: solvent viscosity controlled relaxation of excited states.

In this paper, the first study of cationic cyanine dye Astrazon Orange-R by combined spectroscopic and theoretical investigation is presented. It is shown that molecular modeling of Astrazon Orange-R is in very good agreement with experiment, allowing us to gain insight into its complicated photophysics. A solvent viscosity controlled relaxation of excited states, involving cyanine isomerization, is also outlined.

One-Pot Three-Step Polymerization System Using Double Click Michael Addition and Radical Photopolymerization.

A click chemistry synthetic strategy based on aza-Michael addition and radical photopolymerization is proposed to generate a polymeric network via three time-controlled steps. The selection of primary diamines and diacrylates allows two consecutive aza-Michael reactions to occur. This reaction sequence affords the unique opportunity to interpose a radical photopolymerization reaction, enhancing the cross-link density. Consequently, the second aza-Michael addition appears as a valuable postconsolidation step of the polymer network.

High performance photoinitiating systems for holography recording: need for a full control of primary processes.

Optimization of holography recording in photopolymers was studied from the point of view of a quite general process, that is, the photogeneration of radicals. On the basis of a dye/coinitiator photoinitiating system, the effect of primary events and their relative efficiency was investigated with respect to the final overall properties, such as the diffraction efficiency. Quenching of the dye excited states by the borate salts coinitiators exhibits important differences depending on the dye used (Rose Bengal or Safranine O). Keeping in mind that both singlet and triplet states of the dyes can react, and taking into account the viscosity of the matrix, a method to evaluate the overall quantum yield of radicals released is proposed. It is found that this quantum yield well correlates with the maximum rate of photopolymerization. More interestingly, the dose required to obtain a given diffraction efficiency was found to be also governed by the radical quantum yield, showing that the final property is directly governed by primary events. This shed some light on the efficiency of photochemical pathway to generate radicals for use in organic or polymer areas.

Tailoring of organic dyes with oxidoreductive compounds to obtain photocyclic radical generator systems exhibiting photocatalytic behavior.

The combination of a dye which absorbs the photon, an electron acceptor and an electron donor leading to energy conversion through electron transfer, was the basis of the so called three-component systems. In this paper, an experimental work combining Rose bengal dye with a triazine derivative as electron acceptor and ethyl 4-(dimethylamino)benzoate as electron donor, will underline the benefit of the photocyclic behavior of three-component systems leading to the dye regeneration. A thermodynamic approach of the photocycle is presented, followed by a mechanistic and computational study of ideal photocycles, in order to outline the specific kinetics occuring in so called photocatalytic systems. The simple kinetic model used is enough to outline the benefit of the cyclic system and to give the basic requirements in term of chemical combination needed to be fulfilled in order to obtain a photocatalytic behavior.

One-component thioxanthone acetic acid derivative photoinitiator for free radical polymerization.

Acetic acid-based thioxanthone (TXCH2 COOH) was synthesized and characterized and used as a photoinitiator for free radical photopolymerization of methyl methacrylate (MMA) in the absence and presence of a tertiary amine (MDEA) in different solvents. Different absorption properties were observed depending on the solvent. Fluorescence and phosphorescence experiments were also carried out successfully. The fluorescence quantum yield was found to be 0.09 and the phosphorescence lifetime was calculated as 138 ms at 77 K. The photoinitiator undergoes efficient intersystem crossing into the triplet state and the lowest triplet state possesses π-π* configuration. Laser flash photolysis experiments show that transient absorption of TXCH2 COOH is similar to the parent thioxanthone and the triplet lifetime was calculated as 2.3 µs at 630 nm.

Squarylium-triazine dyad as a highly sensitive photoradical generator for red light.

New dyads, based on squarylium dye and substituted-triazine, were synthesized that exhibit an intramolecular photodissociative electron-transfer reaction. The compounds were used as a red-light photoradical generator. The photochemical activity of the dyad was compared to the corresponding unlinked systems (S+T) by determining the rate constant of electron transfer. The efficiency of the radical generation from the dyad compared to the unlinked system was demonstrated by measuring the maximum rate of free radical polymerization of acrylates in film. An excellent relationship between the rate of electron transfer and the rate of polymerization was found, evidencing the interest of this new approach to efficiently produce radicals under red light.