High Photoinitiating Efficiency of Benzothioxanthene-based Oxime Esters in Photopolymerization via Photocleavage and/or Single Electron Transfer under Visible Light and Sunlight.

In this work, six benzothioxanthene-based oxime esters were employed as photoinitiators for photopolymerization with visible light (LED) and sunlight. Their abilities to behave as Type I photoinitiators by mean of a photocleavage mechanism of oxime esters but also in multicomponent photoinitiating system with an iodonium salt (through an electron transfer mechanism) were both explored with the different structures. Due to their broad absorption spectra tailing up 600 nm, photoinitiating properties of the benzothioxanthene-based oxime esters were systematically tested under excitation with low-intensity LED light at wavelengths of 405 nm and 450 nm. Additionally, to the polymerization tests done under artificial light, different benzothioxanthene-based oxime esters were also investigated as solar photoinitiators and displayed a high reactivity in France (Western Europe) even in winter conditions. For the best candidates i.e. the most reactive structures, direct laser write experiments were carried out, evidencing the interest of these structures.

Novel High-Performance Glyoxylate Derivative-Based Photoinitiators for Free Radical Photopolymerization and 3D Printing with Visible LED.

Investigations concerning the glyoxylate moiety as a photocleavable functional group for visible light photoinitiators, particularly in the initiation of free radical photopolymerization remain limited. This study introduces nine innovative carbazole-based ethyl glyoxylate derivatives (CEGs), which are synthesized and found to exhibit excellent photoinitiation abilities as monocomponent photoinitiating systems. Notably, these structures demonstrate robust absorption in the near-UV/visible range, surpassing the commercial photoinitiators. Moreover, the newly developed glyoxylate derivatives show higher acrylate function conversions compared to a benchmark photoinitiator (MBF) in free radical photopolymerization. Elucidation of the photoinitiation mechanism of CEGs is achieved through a comprehensive analysis involving the decarboxylation reaction and electron spin resonance spin trapping. Furthermore, their practical utility is confirmed during direct laser writing and 3D printing processes, enabling the successful fabrication of 3D printed objects. This study introduces pioneering concepts and effective strategies in the molecular design of novel photoinitiators, showcasing their potential for highly advantageous applications in 3D printing.

Ultrafast Sunlight-Induced Polymerization: Unveiling 2-Phenylnaphtho[2,3-d]Thiazole-4,9-dione as a Unique Scaffold for High-Speed and Precision 3D Printing.

A series of 15 dyes based on the 2-phenylnaphtho[2,3-d]thiazole-4,9-dione scaffold and 1 compound based on the 2,3-diphenyl-1,2,3,4-tetrahydrobenzo[g]quinoxaline-5,10-dione scaffold are studied as photoinitiators. These compounds are used in two- and three-component high-performance photoinitiating systems for the free radical polymerization of trimethylolpropane triacrylate (TMPTA) and polyethylene glycol diacrylate (PEGDA) under sunlight. Remarkably, the conversion of TMPTA can reach ≈60% within 20 s, while PEGDA attains a 96% conversion within 90 s. To delve into the intricate chemical mechanisms governing the polymerization, an array of analytical techniques is employed. Specifically, UV-vis absorption and fluorescence spectroscopy, steady-state photolysis, stability experiments, fluorescence quenching experiments, cyclic voltammetry, and electron spin resonance spin trapping (ESR-ST) experiments, collectively contribute to a comprehensive understanding of the photochemical mechanisms. Photoinitiation capacities of these systems are determined using real-time Fourier transformed infrared spectroscopy (RT-FTIR). Of particular interest is the revelation that, owing to the superior initiation ability of these dyes, high-resolution 3D patterns can be manufactured by direct laser write (DLW) technology and 3D printing. This underscores the efficient initiation of free radical polymerization processes by the newly developed dyes under both artificial and natural light sources, presenting an avenue for energy-saving, and environmentally friendly polymerization conditions.

Recent Advances in Monocomponent Visible Light Photoinitiating Systems Based on Sulfonium Salts.

During the last decades, multicomponent photoinitiating systems have been the focus of intense research efforts, especially for the design of visible light photoinitiating systems. Although highly reactive three-component and even four-component photoinitiating systems have been designed, the complexity to elaborate such mixtures has incited researchers to design monocomponent Type II photoinitiators. Using this approach, the photosensitizer and the radical/cation generator can be combined within a unique molecule, greatly simplifying the elaboration of the photocurable resins. In this field, sulfonium salts are remarkable photoinitiators but these structures lack absorption in the visible range. Over the years, various structural modifications have been carried out in order to redshift their absorptions in the visible region. In this work, an overview of the different sulfonium salts activable under visible light and reported to date is proposed.

5,12-Dihydroindolo[3,2-a]Carbazole Derivatives-Based Water Soluble Photoinitiators for 3D Antibacterial Hydrogels Preparation.

Indolo[3,2-a]carbazole alkaloids have drawn a growing interest in recent years owing to their potential electrical and optical properties. With 5,12-dihydroindolo[3,2-a]carbazole serving as the scaffold, two novel carbazole derivatives are synthesized in this study. Both compounds are extremely soluble in water, with solubility surpassing 7% in weight. Intriguingly, the introduction of aromatic substituents contributed to drastically reduce the π-stacking ability of carbazole derivatives, while the presence of the sulfonic acid groups enables the resulting carbazoles remarkably soluble in water, allowing them to be used as especially efficient water-soluble PIs in conjunction with co-initiators, i.e., triethanolamine and the iodonium salt, respectively, employed as electron donor and acceptor. Surprisingly, multi-component photoinitiating systems based on these synthesized carbazole derivatives could be used for the in situ preparation of hydrogels containing silver nanoparticles via laser write procedure with a light emitting diode (LED)@405 nm as light source, and the produced hydrogels display antibacterial activity against Escherichia coli.

Self-assembly of s-indacene-tetrone on Cu(111): molecular trapping and patterning of Cu adatoms.

The supramolecular self-assembly of s-indacene-1,3,5,7(2H,6H)-tetrone on the Cu(111) surface was investigated under ultrahigh vacuum by room-temperature scanning tunneling microscopy supported by theoretical modelling based on density functional theory. In total, six different phases were found, driven by hydrogen bonding, metal ligand coordination or covalent coupling. Host-guest interactions allowed for the accommodation of molecular or metal clusters inside the open nanoporous patterns. In one phase, molecular trapping was stochastically observed inside the large periodic nanopores created inside the supramolecular network. The three metal-organic networks observed resulted in the creation of different kinds of regular arrays of isolated metal adatoms or adatom clusters with a lattice period larger than 1 nm.

Synthesis and Optical Properties of a Series of Push-Pull Dyes Based on Pyrene as the Electron Donor.

Fifteen push-pull dyes comprising the tetracyclic polyaromatic pyrene have been designed and synthesized. The optical properties of the fifteen dyes have been examined in twenty-two solvents of different polarities. Surprisingly, contrarily to what is classically observed for push-pull dyes of D-π-A structures, a negative solvatochromism could be found for numerous dyes. The photoluminescence and thermal properties of the dyes were also examined. Theoretical calculations were carried out to support the experimental results.

Indane-1,3-Dione: From Synthetic Strategies to Applications.

Indane-1,3-dione is a versatile building block used in numerous applications ranging from biosensing, bioactivity, bioimaging to electronics or photopolymerization. In this review, an overview of the different chemical reactions enabling access to this scaffold but also to the most common derivatives of indane-1,3-dione are presented. Parallel to this, the different applications in which indane-1,3-dione-based structures have been used are also presented, evidencing the versatility of this structure.

On-Surface Synthesis of Unsaturated Hydrocarbon Chains through C-S Activation.

We use an on-surface synthesis approach to drive the homocoupling reaction of a simple dithiophenyl-functionalized precursor on Cu(111). The C-S activation reaction is initiated at low annealing temperature and yields unsaturated hydrocarbon chains interconnected in a fully conjugated reticulated network. High-resolution atomic force microscopy imaging reveals the opening of the thiophenyl rings and the presence of trans- and cis-oligoacetylene chains as well as pentalene units. The chemical transformations were studied by C 1s and S 2p core level photoemission spectroscopy and supported by theoretical calculations. At higher annealing temperature, additional cyclization reactions take place, leading to the formation of small graphene flakes.

Novel Copper Complexes as Visible Light Photoinitiators for the Synthesis of Interpenetrating Polymer Networks (IPNs).

This work is devoted to the study of two copper complexes (Cu) bearing pyridine ligands, which were synthesized, evaluated and tested as new visible light photoinitiators for the free radical photopolymerization (FRP) of acrylates functional groups in thick and thin samples upon light-emitting diodes (LED) at 405 and 455 nm irradiation. These latter wavelengths are considered to be safe to produce polymer materials. The photoinitiation abilities of these organometallic compounds were evaluated in combination with an iodonium (Iod) salt and/or amine (e.g., N-phenylglycine-NPG). Interestingly, high final conversions and high polymerization rates were obtained for both compounds using two and three-component photoinitiating systems (Cu1 (or Cu2)/Iodonium salt (Iod) (0.1%/1% w/w) and Cu1 (or Cu2)/Iod/amine (0.1%/1%/1% w/w/w)). The new proposed copper complexes were also used for direct laser write experiments involving a laser diode at 405 nm, and for the photocomposite synthesis with glass fibers using a UV-conveyor at 395 nm. To explain the obtained polymerization results, different methods and characterization techniques were used: steady-state photolysis, real-time Fourier transform infrared spectroscopy (RT-FTIR), emission spectroscopy and cyclic voltammetry.

Improving Orientation, Packing Density, and Molecular Arrangement in Self-Assembled Monolayers of Bianchoring Ferrocene-Triazole Derivatives by "Click" Chemistry.

This work describes the self-assembled monolayers (SAMs) of two ferrocene derivatives with two anchoring groups (at the bottom and at the top of the SAM) deposited on ultraflat template-stripped gold substrates by cyclic voltammetry and analyzed by complementary surface characterization techniques. The SAM of each molecule is deposited by three different protocols: direct deposition (one step), click reaction on the surface (two steps), and reverse click reaction on the surface (two steps). The SAM structure is well studied to determine the SAM orientation, SAM arrangement, and ferrocene position within the SAM. Electron transfer kinetics have also been studied, which agree with the quality of each SAM. With the help of two anchoring groups and click-chemistry active functional groups, we have shown that the two molecules can be deposited by controlling the position of ferrocene at either end. We further investigated the involvement of the triazole five-membered ring in the electron transfer mechanism. We have found that a carbon spacer between ferrocene and triazole improves the SAM packing. This study enhances the understanding of tethering thiol and thiol acetate anchoring groups on gold by a controlled orientation, which may help in the development of functional molecular devices requiring two anchoring groups.

Enantioselective Radical Reactions Using Chiral Catalysts.

Benefiting from the impressive increase in fundamental knowledge, the last 20 years have shown a continuous burst of new ideas and consequently a plethora of new catalytic methods for enantioselective radical reactions. This review aims to provide a complete survey of progress achieved over this latter period. The first part of this review focuses on the use of chiral organocatalysts, and these include catalysts covalently linked to the substrate and those that interact with the substrate by weaker interactions like hydrogen bonds. The second part of the review is devoted to transition-metal redox catalysis which is organized according to increasing atomic number for the first-row transition metals (Ti, Cr, Fe, Mn, Co, Ni, Cu). Bioinspired manganese- and iron-mediated hydroxylations and oxidations are also discussed. A specific section is dedicated to the reactivity of Ru, Rh, and Ir complexes as Lewis acids with a special focus on complexes chiral at metal. Absorption of photons result in different events such as energy transfer, single-electron transfer, and hydrogen-atom transfer facilitating the formation of radicals. Organocatalysis has been successfully combined with photocatalysts, a reactivity which has opened new pathways enlarging the number of radical precursors available. The merger of photocatalysis with organo- or metalla-photocatalysis has brought novelty and allowed for the discovery of a large number of original transformations. The use of enzyme-catalyzed reactions involving radical intermediates which also largely benefit from visible-light irradiation are included in the review. This review provides a comprehensive inventory of progress in enantioselective radical reactions with a goal of detailing the reaction mechanisms involved in these transformations such that any nonspecialist could find their own creativity to invent yet unknown applications.

Water-Soluble Visible Light Sensitive Photoinitiating System Based on Charge Transfer Complexes for the 3D Printing of Hydrogels.

The development of visible-light 3D printing technology by using water-soluble initiating systems has attracted widespread attention due to their potential applications in the manufacture of hydrogels. Besides, at present, the preparation of water-soluble photoinitiators suitable for visible light irradiation (such as LEDs) still remains a challenge. Therefore, this work is devoted to developing water-soluble photoinitiators (PI)/photoinitiating systems (PIS) upon irradiation with a LED @ 405 nm. In detail, a new water-slightly-soluble chalcone derivative dye [(E)-3-(4-(dimethylamino) phenyl)-1-(4-(2-(2-(2-methoxyethoxy) ethoxy) ethoxy) phenyl) prop-2-en-1-one] was synthesized here and used as a PI with a water-soluble coinitiator, i.e., triethanolamine (TEA) which was also used as an electron donor. When combined together, a charge transfer complex (CTC) formed immediately which exhibited excellent initiating ability for the free radical photopolymerization of poly(ethyleneglycol)diacrylate (PEG-DA). In light of the powerful CTC effect, the [dye-TEA] CTC could not only exhibit enhanced water solubility and mechanical properties but could also be effectively applied for 3D printing. This CTC system is environmentally friendly and cost-saving which demonstrates a great potential to prepare hydrogels via photopolymerization.

Towards new NIR dyes for free radical photopolymerization processes.

The use of cheap and safe near-infrared (NIR) light is still the subject of intense research efforts but remains a huge challenge due to the associated low photon energy (wavelength from 0.78 to 2.5 µm). In this study, a series of 17 NIR dyes mainly based on a well-established cyanine scaffold is proposed. Remarkably, 11 of them were never synthesized before. Markedly, noncharged structures, negatively charged cyanine bearing Na+ as counter cation, and positively charged cyanines bearing (B(Ph)4 -) or (I-) as counter anions were examined as promising NIR light photoinitiating systems. Excellent photoinitiating abilities were found for some reported dyes when used in combination with iodonium salt and amine. Markedly, photothermal effects with a huge heater behavior were also observed for different NIR dye structures. Interestingly, the synthesis of interpenetrating polymer networks (IPNs, e.g., for the polymerization of acrylate/epoxy monomer blends) can also be carried out upon NIR light with the proposed systems.

Recent Advances in bis-Chalcone-Based Photoinitiators of Polymerization: From Mechanistic Investigations to Applications.

Over the past several decades, photopolymerization has become an active research field, and the ongoing efforts to develop new photoinitiating systems are supported by the different applications in which this polymerization technique is involved-including dentistry, 3D and 4D printing, adhesives, and laser writing. In the search for new structures, bis-chalcones that combine two chalcones' moieties within a unique structure were determined as being promising photosensitizers to initiate both the free-radical polymerization of acrylates and the cationic polymerization of epoxides. In this review, an overview of the different bis-chalcones reported to date is provided. Parallel to the mechanistic investigations aiming at elucidating the polymerization mechanisms, bis-chalcones-based photoinitiating systems were used for different applications, which are detailed in this review.

Nitro-Carbazole Based Oxime Esters as Dual Photo/Thermal Initiators for 3D Printing and Composite Preparation.

A series of Type I photoinitiators (PIs) based on a nitrocarbazole scaffold are developed and examined for the first time as photoinitiators for visible light photopolymerization. Three oxime esters (OXE-M, OXE-V, OXE-P) varying by the terminal groups (acetyl, acryloyl and benzoyl) attached via the oxime ester group are originally prepared. As a result of this, the three PIs exhibit excellent photoinitiation abilities in the presence of acrylate monomers upon LED@ 405 nm irradiation. Markedly, OXE-M exhibits a better performance than the benchmark Type I phosphine-oxide (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide TPO). Chemical mechanisms supporting the polymerization process with these PIs are investigated by steady state photolysis, molecular orbital calculations and real-time Fourier transformed infrared spectroscopy. After the cleavage of N─O bond and decarboxylation, free radicals are generated to initiate the free radical polymerization efficiently. Free radical photopolymerization of OXE-M is applied in direct laser write and 3D printing. Interestingly, OXE-M exhibits thermal initiation behaviors in monomers and can be used as dual photo and thermal initiators. The highly opaque feature of carbon fibers makes it difficult for light penetration, so dual photo/thermal curing are used here to prepare carbon fiber composites.

3-Carboxylic Acid and Formyl-Derived Coumarins as Photoinitiators in Photo-Oxidation or Photo-Reduction Processes for Photopolymerization upon Visible Light: Photocomposite Synthesis and 3D Printing Applications.

In this paper, nine organic compounds based on the coumarin scaffold and different substituents were synthesized and used as high-performance photoinitiators for free radical photopolymerization (FRP) of meth(acrylate) functions under visible light irradiation using LED at 405 nm. In fact, these compounds showed a very high initiation capacity and very good polymerization profiles (both high rate of polymerization (Rp) and final conversion (FC)) using two and three-component photoinitiating systems based on coum/iodonium salt (0.1%/1% w/w) and coum/iodonium salt/amine (0.1%/1%/1% w/w/w), respectively. To demonstrate the efficiency of the initiation of photopolymerization, several techniques were used to study the photophysical and photochemical properties of coumarins, such as: UV-visible absorption spectroscopy, steady-state photolysis, real-time FTIR, and cyclic voltammetry. On the other hand, these compounds were also tested in direct laser write experiments (3D printing). The synthesis of photocomposites based on glass fiber or carbon fiber using an LED conveyor at 385 nm (0.7 W/cm2) was also examined.

Near-Infrared PhotoInitiating Systems: Photothermal versus Triplet-Triplet Annihilation-Based Upconversion Polymerization.

NIR light-induced polymerization has attracted more and more attention in the photopolymerization field due to the possibility to use safer and more penetrating wavelengths, reducing the hazardousness. Here, a novel perspective for the free radical polymerization of acrylate-based monomers based on triplet-triplet annihilation upconversion (TTA-UC) is proposed, avoiding the introduction of heavy metals, usually required in the TTA processes. Thermal imaging experiments and Fourier transform infrared spectroscopy are respectively used to record the temperature during NIR irradiation and measure the reactive function conversion. The competition between the TTA-UC and the NIR photothermal activation is investigated to compare the relative efficiency of both NIR processes. In view of the results obtained by the different methods, the photothermal effect seems to get the upper hand over the photoactivation of the system.

Sub-ppb mercury detection in real environmental samples with an improved rhodamine-based detection system.

A new procedure is described for the determination of Hg2+ ions in water samples. A Rhodamine based fluorescent sensor was synthesized and the experimental conditions were specifically optimized for application to environmental samples, which requires low detection limits and high selectivity in competitive experiments with realistic concentrations of other metal ions. Incorporation of a Rhodamine-6G fluorophore to a previously described sensor and optimization of the buffer system (detection with acetic acid at pH 5.25) enabled significant enhancement of the sensitivity (detection limit = 0.27 µg L-1) and selectivity. The optimized procedure using high-throughput microplates has been applied to tap and river waters with good results.

Novel Photoinitiators Based on Benzophenone-Triphenylamine Hybrid Structure for LED Photopolymerization.

In this study, a new generation of photoinitiator (PI) based on hybrid structures combining benzophenone and triphenylamine is proposed. Remarkably, these photoinitiators (noted monofunctional benzophenone-triphenylamine (MBP-TPA) and trifunctional benzophenone-triphenylamine (TBP-TPA)) are designed and developed for the photopolymerization under light-emitting diodes (LEDs). Benzoyl substituents connected with triphenylamine moiety contribute to the excellent absorption properties which results in both high final conversions and polymerization rates in free radical photopolymerization (FRP). Remarkably, TBP-TPA owning trifunctional benzophenone group exhibits a better Type II PI behavior than well-known 2-isopropylthioxanthone for photopolymerization under LED@365 and 405 nm irradiation. FRP and cationic photopolymerization of TBP-TPA-based systems are applied on 3D printing experiments, and good profiles of the 3D patterns are observed. The high molecular weight of TBP-TPA associated with it trifunctional character can also be very interesting for a better migration stability of PIs that is a huge challenge. The development of this new generation of photoinitiators based on benzophenone hybrid structures is a real breakthrough. It reveals that the novel versatile photoinitiators based on benzophenone-triphenylamine hybrid structures have great potentials for future industrial applications (e.g., 3D printing, composites, etc.).