A mixture of oppositely charged polymer and surfactants changes the solubilized state, having a complex precipitation region at the composition of electric neutralization. This complex behavior has ...been applied to surface modification in the fields of health care and cosmetic products such as conditioning shampoos, as a dilution-deposition system in which the polymer/surfactant mixture at the higher surfactant concentration precipitates the insoluble complex by dilution. A large number of studies over many years have revealed the basic coacervation behavior and physicochemical properties of complexes. However, the mechanism by which a precipitated complex performs surface modification is not well understood. The precipitation region and the morphology of precipitated complex that are changed by molecular structure and additives affect the performance. Hydrophilic groups such as the EO unit in polymers and surfactants, the mixing of nonionic or amphoteric surfactant and nonionic polymer, and the addition of low polar solvent influence the complex precipitation region. Furthermore, the morphology of precipitated complex is formed by crosslinking and aggregating among polymers in the dilution process, and characterizes the performance of products. The polymer chain density in precipitated complex is determined by the charges of both the polymer and surfactant micelle and the conformation of polymer. As a result, the morphology of precipitated complexes is changed from a closely packed film to looser meshes, and/or to small particles, and it is possible for the morphology to control the rheological properties and the amount of adsorbed silicone. In the future, further investigation of the relationships between the morphology and performance is needed.
Morphology changes by polymer and surfactant charges for the complex precipitated from the 10 times diluted model shampoo (1% Cat-HEC, 15% LES/LPB and 3% salt). Data taken from ref. 17. Display omitted
•Updates on characterization of oppositely charged polymer/surfactant complex in dilution deposition system.•Effect of molecular structure and additives on complex precipitation behavior•Changes of resolubilized complexes in the dilution process•Morphology and character of complex in the precipitation region
The development of photoinduced organocatalyzed atom transfer radical polymerization (O-ATRP) has received considerable attention since its introduction in 2014. Expanding on many of the advantages ...of traditional ATRP, O-ATRP allows well-defined polymers to be produced under mild reaction conditions using organic photoredox catalysts. As a result, O-ATRP has opened access to a range of sensitive applications where the use of a metal catalyst could be of concern, such as electronics, certain biological applications, and the polymerization of coordinating monomers. However, key limitations of this method remain and necessitate further investigation to continue the development of this field. As such, this review details the achievements made to-date as well as future research directions that will continue to expand the capabilities and application landscape of O-ATRP.
Atom transfer radical polymerization (ATRP) has become one of the most implemented methods for polymer synthesis, owing to impressive control over polymer composition and associated properties. ...However, contamination of the polymer by the metal catalyst remains a major limitation. Organic ATRP photoredox catalysts have been sought to address this difficult challenge but have not achieved the precision performance of metal catalysts. Here, we introduce diaryl dihydrophenazines, identified through computationally directed discovery, as a class of strongly reducing photoredox catalysts. These catalysts achieve high initiator efficiencies through activation by visible light to synthesize polymers with tunable molecular weights and low dispersities.
C–N cross-coupling is an important class of reactions with far-reaching impacts across chemistry, materials science, biology, and medicine. Transition metal complexes can elegantly orchestrate ...diverse aminations but typically require demanding reaction conditions, precious metal catalysts, or oxygen-sensitive procedures. Here, we introduce a mild nickel-catalyzed C–N cross-coupling methodology that operates at room temperature using an inexpensive nickel source (NiBr2·3H2O), is oxygen tolerant, and proceeds through direct irradiation of the nickel–amine complex. This operationally robust process was employed for the synthesis of diverse C–N-coupled products (40 examples) by irradiating a solution containing an amine, an aryl halide, and a catalytic amount of NiBr2·3H2O with a commercially available 365 nm LED at room temperature without added photoredox catalyst and the amine substrate serving additional roles as the ligands and base. Density functional theory calculations and kinetic isotope effect experiments were performed to elucidate the observed C–N cross-coupling reactivity.
Dual catalytic light-driven cross-coupling methodologies utilizing a Ni(II) salt with a photocatalyst (PC) have emerged as promising methodologies to forge aryl C–N bonds under mild conditions. The ...recent discovery that the PC can be omitted and the Ni(II) complex directly photoexcited suggests that the PC may perform energy transfer (EnT) to the Ni(II) complex, a mechanistic possibility that has recently been proposed in other systems across dual Ni photocatalysis. Here, we report the first studies in this field capable of distinguishing EnT from electron transfer (ET), and the results are consistent with Förster-type EnT from the excited state Ru(bpy)3Cl2 PC to Ni-amine complexes. The structure and speciation of Ni-amine complexes that are the proposed EnT acceptors were elucidated by crystallography and spectroscopic binding studies. With the acceptors known, quantitative Förster theory was utilized to predict the ratio of quenching rate constants upon changing the PC, enabling selection of an organic phenoxazine PC that proved to be more effective in catalyzing C–N cross-coupling reactions with a diverse selection of amines and aryl halides.
Photoinduced controlled radical polymerizations (CRPs) have provided a variety of approaches for the synthesis of polymers possessing targeted structures, compositions, and functionalities with the ...added capability for spatial and temporal control, presenting the potential for new materials development. However, the scalability and reliability of these systems can be limited as a consequence of dependence on uniform irradiation of the reaction to produce well-defined products. In this perspective, we highlight the utility and promise of photo-CRP approaches through an overview of the adaptation of these methodologies to photo-flow reactor systems. Special emphasis is placed on the current state-of-the-art in polymerization scalability, reactor design, and polymer scope.
The Birch reduction is a powerful synthetic methodology that uses solvated electrons to convert inert arenes to 1,4-cyclohexadienesvaluable intermediates for building molecular complexity. Birch ...reductions traditionally employ alkali metals dissolved in ammonia to produce a solvated electron for the reduction of unactivated arenes such as benzene (E red < −3.42 V vs SCE). Photoredox catalysts have been gaining popularity in highly reducing applications, but none have been reported to demonstrate reduction potentials powerful enough to reduce benzene. Here, we introduce benzoghiperylene imides as new organic photoredox catalysts for Birch reductions performed at ambient temperature and driven by visible light from commercially available LEDs. Using low catalyst loadings (<1 mol percent), benzene and other functionalized arenes were selectively transformed to 1,4-cyclohexadienes in moderate to good yields in a completely metal-free reaction. Mechanistic studies support that this unprecedented visible-light-induced reactivity is enabled by the ability of the organic photoredox catalyst to harness the energy from two visible-light photons to affect a single, high-energy chemical transformation.
Through the study of structure–property relationships using a combination of experimental and computational analyses, a number of phenoxazine derivatives have been developed as visible ...light absorbing, organic photoredox catalysts (PCs) with excited state reduction potentials rivaling those of highly reducing transition metal PCs. Time-dependent density functional theory (TD-DFT) computational modeling of the photoexcitation of N-aryl and core modified phenoxazines guided the design of PCs with absorption profiles in the visible regime. In accordance with our previous work with N,N-diaryl dihydrophenazines, characterization of noncore modified N-aryl phenoxazines in the excited state demonstrated that the nature of the N-aryl substituent dictates the ability of the PC to access a charge transfer excited state. However, our current analysis of core modified phenoxazines revealed that these molecules can access a different type of CT excited state which we posit involves a core substituent as the electron acceptor. Modification of the core of phenoxazine derivatives with electron-donating and electron-withdrawing substituents was used to alter triplet energies, excited state reduction potentials, and oxidation potentials of the phenoxazine derivatives. The catalytic activity of these molecules was explored using organocatalyzed atom transfer radical polymerization (O-ATRP) for the synthesis of poly(methyl methacrylate) (PMMA) using white light irradiation. All of the derivatives were determined to be suitable PCs for O-ATRP as indicated by a linear growth of polymer molecular weight as a function of monomer conversion and the ability to synthesize PMMA with moderate to low dispersity (dispersity less than or equal to 1.5) and initiator efficiencies typically greater than 70% at high conversions. However, only PCs that exhibit strong absorption of visible light and strong triplet excited state reduction potentials maintain control over the polymerization during the entire course of the reaction. The structure–property relationships established here will enable the application of these organic PCs for O-ATRP and other photoredox-catalyzed small molecule and polymer syntheses.
N-Aryl phenoxazines have been synthesized and introduced as strongly reducing metal-free photoredox catalysts in organocatalyzed atom transfer radical polymerization for the synthesis of well-defined ...polymers. Experiments confirmed quantum chemical predictions that, like their dihydrophenazine analogs, the photoexcited states of phenoxazine photoredox catalysts are strongly reducing and achieve superior performance when they possess charge transfer character. We compare phenoxazines to previously reported dihydrophenazines and phenothiazines as photoredox catalysts to gain insight into the performance of these catalysts and establish principles for catalyst design. A key finding reveals that maintenance of a planar conformation of the phenoxazine catalyst during the catalytic cycle encourages the synthesis of well-defined macromolecules. Using these principles, we realized a core substituted phenoxazine as a visible light photoredox catalyst that performed superior to UV-absorbing phenoxazines as well as previously reported organic photocatalysts in organocatalyzed atom transfer radical polymerization. Using this catalyst and irradiating with white LEDs resulted in the production of polymers with targeted molecular weights through achieving quantitative initiator efficiencies, which possess dispersities ranging from 1.13 to 1.31.
Development of photocatalysts (PCs) with diverse properties has been essential in the advancement of organocatalyzed atom transfer radical polymerization (O‐ATRP). Dimethyl dihydroacridines are ...presented here as a new family of organic PCs, for the first time enabling controlled polymerization of challenging acrylate monomers by O‐ATRP. Structure–property relationships for seven PCs are established, demonstrating tunable photochemical and electrochemical properties, and accessing a strongly oxidizing 2PC.+ intermediate for efficient deactivation. In O‐ATRP, the combination of PC, implementation of continuous‐flow reactors, and promotion of deactivation through addition of LiBr are critical to producing well‐defined acrylate polymers with dispersities as low as 1.12. The utility of this approach is established through demonstration of the oxygen‐tolerance of the system and application to diverse acrylate monomers, including the synthesis of well‐defined di‐ and triblock copolymers.
Polymers in flow: Organic photoredox catalysis is applied to the controlled synthesis of poly(acrylates). This advancement is enabled by the development of new organic photoredox catalysts, dimethyl dihydroacridines, with unique properties. The use of continuous flow reactors is also key to the success of the method.
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