Atom transfer radical polymerization (ATRP) with dual photoredox/copper catalysis combines the advantages of photo-ATRP and photoredox-mediated ATRP, utilizing visible light and ensuring broad monomer scope and solvent compatibility while minimizing side reactions. Despite its popularity, challenges include high photocatalyst (PC) loadings (10 to 1000 ppm), requiring additional purification and increasing costs. In this study, we discover a PC that functions at the sub-ppm level for ATRP through mechanism-driven PC design. Through studying polymerization mechanisms, we find that the efficient polymerizations are driven by PCs whose ground state oxidation potential-responsible for PC regeneration-play a more important role than their excited state reducing power, responsible for initiation. This is verified by screening PCs with varying redox potentials and triplet excited state generation capabilities. Based on these findings, we identify a highly efficient PC, 4DCDP-IPN, featuring moderate excited state reducing power and a maximized ground state oxidation potential. Employing this PC at 50 ppb, we synthesize poly(methyl methacrylate) with high conversion, narrow molecular weight distribution, and high chain-end fidelity. This system exhibits oxygen tolerance and supports large-scale reactions under ambient conditions. Our findings, driven by the systematic PC design, offer meaningful insights for controlled radical polymerizations and metallaphotoredox-mediated syntheses beyond ATRP.
We present the strategic design of donor-acceptor cyanoarene-based photocatalysts (PCs) aiming to augment beneficial PC degradation for halogen atom transfer (XAT)-induced dehalogenation reactions. Our investigation reveals a competitive nature between the catalytic cycle and the degradation pathway, with degradation becoming dominant, particularly for less activated alkyl halides. The degradation behavior of PCs significantly impacts the efficiency of the XAT process, leading to exploration into manipulating the degradation behavior in a desirable direction. Recognizing the variation in the nature and rate of PC degradation, as well as its influence on the reaction across the range of PC structures, we carefully engineered the PCs to develop a pre-catalyst, named 3DP-DCDP-IPN. This pre-catalyst undergoes rapid degradation into an active form, 3DP-DCDP-Me-BN, exhibited an enhanced reducing ability in its radical anion form to induce better PC regeneration and consequently effectively catalyzes the XAT reaction, even with a challenging substrate.
In developing an organic light-emitting diode (OLED) panel for a foldable smartphone (specifically, a color filter on encapsulation) aimed at reducing power consumption, the use of a new optically clear adhesive (OCA) that blocks UV light was crucial. However, the incorporation of a UV-blocking agent within the OCA presented a challenge, as it restricted the traditional UV-curing methods commonly used in the manufacturing process. Although a visible-light curing technique for producing UV-blocking OCA was proposed, its slow curing speed posed a barrier to commercialization. Our study introduces a highly efficient photo-initiating system (PIS) for the rapid production of UV-blocking OCAs utilizing visible light. We have carefully selected the photocatalyst (PC) to minimize electron and energy transfer to UV-blocking agents and have chosen co-initiators that allow for faster electron transfer and more rapid PC regeneration compared to previously established amine-based co-initiators. This advancement enabled a tenfold increase in the production speed of UV-blocking OCAs, while maintaining their essential protective, transparent, and flexible properties. When applied to OLED devices, this OCA demonstrated UV protection, suggesting its potential for broader application in the safeguarding of various smart devices.
Novel acrylate monomers, derived from terpenes are synthesized for use in optically clear adhesives (OCAs) suitable for foldable displays. These OCAs are prepared using visible-light-driven polymerization, an eco-friendly method. Through physical, rheological, and mechanical characterization, the prepared OCAs possess low modulus and exhibit outstanding creep and recovery properties, making them suitable for foldable devices.
Lifetime-reconfigurable soft robots have emerged as a new class of robots, emphasizing the unmet needs of futuristic sustainability and security. Trigger-transient materials that can both actuate and degrade on-demand are crucial for achieving life-reconfigurable soft robots. Here, we propose the use of transient and magnetically actuating materials that can decompose under ultraviolet light and heat, achieved by adding photo-acid generator (PAG) and magnetic particles (Sr-ferrite) to poly(propylene carbonate) (PPC). Chemical and thermal analyses reveal that the mechanism of PPC-PAG decomposition occurs through PPC backbone cleavage by the photo-induced acid. The self-assembled monolayer (SAM) encapsulation of Sr-ferrite preventing the interaction with the PAG allowed the transience of magnetic soft actuators. We demonstrate remotely controllable and degradable magnetic soft kirigami actuators using blocks with various magnetized directions. This study proposes novel approaches for fabricating lifetime-configurable magnetic soft actuators applicable to diverse environments and applications, such as enclosed/sealed spaces and security/military devices.
Light-driven 3D printing is gaining significant attention for its unparalleled build speed and high-resolution in additive manufacturing. However, extending vat photopolymerization to multifunctional, photoresponsive materials poses challenges, such as light attenuation and interference between the photocatalysts (PCs) and photoactive moieties. This study introduces novel visible-light-driven acrylic resins that enable rapid, high-resolution photoactive 3D printing. The synergistic combination of a cyanine-based PC, borate, and iodonium coinitiators (HNu 254) achieves an excellent printing rate and feature resolution under low-intensity, red light exposure. The incorporation of novel hexaarylbiimidazole (HABI) crosslinkers allows for spatially-resolved photoactivation upon exposure to violet/blue light. Furthermore, a photobleaching mechanism inhibited by HNu 254 during the photopolymerization process results in the production of optically-clear 3D printed objects. Real-time Fourier transform infrared spectroscopy validates the rapid photopolymerization of the HABI-containing acrylic resin, whereas mechanistic evaluations reveal the underlying dynamics that are responsible for the rapid photopolymerization rate, wavelength-orthogonal photoactivation, and observed photobleaching phenomenon. Ultimately, this visible-light-based printing method demonstrates: (i) rapid printing rate of 22.5 mm h-1, (ii) excellent feature resolution (≈20 µm), and (iii) production of optically clear object with self-healing capability and spatially controlled cleavage. This study serves as a roadmap for developing next-generation "smart" 3D printing technologies.
With growing sustainability concerns, the need for products that facilitate easy disassembly and reuse has increased. Adhesives, initially designed for bonding, now face demands for selective removal, enabling rapid assembly-disassembly and efficient maintenance across industries. This need is particularly evident in the display industry, with the rise of foldable devices necessitating specialized adhesives. A novel optically clear adhesive (OCA) is presented for foldable display, featuring a unique UV-stimulated selective removal feature. This approach incorporates benzophenone derivatives into the polymer network, facilitating rapid debonding under UV irradiation. A key feature of this method is the adept use of visible-light-driven radical polymerization for OCA film fabrication. This method shows remarkable compatibility with various monomers and exhibits orthogonal reactivity to benzophenone, rendering it ideal for large-scale production. The resultant OCA not only has high transparency and balanced elasticity, along with excellent resistance to repeated folding, but it also exhibits significantly reduced adhesion when exposed to UV irradiation. By merging this customized formulation with strategically integrated UV-responsive elements, an effective solution is offered that enhances manufacturing efficiency and product reliability in the rapidly evolving field of sustainable electronics and displays. This research additionally contributes to eco-friendly device fabrication, aligning with emerging technology demands.
Thermally activated delayed fluorescence (TADF) emitters are molecules of interest as homogeneous organic photocatalysts (OPCs) for photoredox chemistry. Here, three classes of OPC candidates are studied in dichloromethane (DCM) or N,N-dimethylformamide (DMF) solutions, using transient absorption spectroscopy and time-resolved fluorescence spectroscopy. These OPCs are benzophenones with either carbazole (2Cz-BP and 2tCz-BP) or phenoxazine/phenothiazine (2PXZ-BP and 2PTZ-BP) appended groups and the dicyanobenzene derivative 4DP-IPN. Dual lifetimes of the S1 state populations are observed, consistent with reverse intersystem crossing (RISC) and TADF emission. Example fluorescence lifetimes in DCM are (5.18 ± 0.01) ns and (6.22 ± 1.27) µs for 2Cz-BP, (1.38 ± 0.01) ns and (0.32 ± 0.01) µs for 2PXZ-BP, and (2.97 ± 0.01) ns and (62.0 ± 5.8) µs for 4DP-IPN. From ground state bleach recoveries and time-correlated single photon counting measurements, triplet quantum yields in DCM are estimated to be 0.62 ± 0.16, 0.04 ± 0.01, and 0.83 ± 0.02 for 2Cz-BP, 2PXZ-BP, and 4DP-IPN, respectively. 4DP-IPN displays similar photophysical behavior to the previously studied OPC 4Cz-IPN. Independent of the choice of solvent, 4DP-IPN, 2Cz-BP, and 2tCz-BP are shown to be TADF emitters, whereas emission by 2PXZ-BP and 2PTZ-BP depends on the molecular environment, with TADF emission enhanced in aggregates compared to monomers. Behavior of this type is representative of aggregation-induced emission luminogens (AIEgens).
The complex photokinetics of donor-acceptor-donor triads with varying flexible spacer lengths (n = 4-10 carbon atoms) are investigated in liquid and solid solution, as well as in crystals, by steady-state and transient fluorescence spectroscopy combined with computational studies. For the short spacer (n = 4) in a liquid solution, dynamic charge-transfer (CT) state formation with subsequent, efficient exciplex emission is observed, effectively competing with quenching through electron transfer (eT) via a radical ion pair. In a solid solution, a fluorescent CT static complex is formed upon freezing for all spacer lengths. This allows the observations of a former seminal report on stimuli-responsive high-contrast fluorescence on/off switching in films of the triads to be reassigned (Adv. Mater. 2012, 24, 5487), now providing a holistic picture on varying spacer length. In fact, external stimuli of the film by modulating the geometry of the CT complex, which results in on/off fluorescence switching (for n > 4) or in a change of the emission color (n = 4). The work thus demonstrates how in-depth analysis of complex photophysics can be put to practical use in materials science.
In this review, we provide a brief history, progress, and applications, and discuss the remaining challenges of photocontrolled reversible addition-fragmentation chain transfer (RAFT) polymerization (i.e., photoinduced electron/energy transfer-RAFT (PET-RAFT), photoiniferter, and photomediated cationic RAFT polymerization). Among these, visible-light-driven RAFT polymerization has attracted particular attention in recent years due to its benefits, including low energy consumption and the safe reaction procedure. Moreover, the incorporation of visible-light photocatalysis in the polymerization has conferred attractive features, such as spatiotemporal control and oxygen tolerance; however, a clear understanding of the reaction mechanism has not been completely provided. We also present recent research efforts to elucidate the polymerization mechanisms with the aid of quantum chemical calculations combined with experimental evidence. This review offers an insight into the better design of polymerization systems for desired applications and helps realize the full potential of photocontrolled RAFT polymerization in both academic- and industrial-scale applications.
Cyanoarene-based photocatalysts (PCs) have attracted significant interest owing to their superior catalytic performance for radical anion mediated photoredox catalysis. However, the factors affecting the formation and degradation of cyanoarene-based PC radical anion (PCâ¢â) are still insufficiently understood. Herein, we therefore investigate the formation and degradation of cyanoarene-based PCâ¢â under widely-used photoredox-mediated reaction conditions. By screening various cyanoarene-based PCs, we elucidate strategies to efficiently generate PCâ¢â with adequate excited-state reduction potentials (Ered*) via supra-efficient generation of long-lived triplet excited states (T1). To thoroughly investigate the behavior of PCâ¢â in actual photoredox-mediated reactions, a reductive dehalogenation is carried out as a model reaction and identified the dominant photodegradation pathways of the PCâ¢â. Dehalogenation and photodegradation of PCâ¢â are coexistent depending on the rate of electron transfer (ET) to the substrate and the photodegradation strongly depends on the electronic and steric properties of the PCs. Based on the understanding of both the formation and photodegradation of PCâ¢â, we demonstrate that the efficient generation of highly reducing PCâ¢â allows for the highly efficient photoredox catalyzed dehalogenation of aryl/alkyl halides at a PC loading as low as 0.001 mol% with a high oxygen tolerance. The present work provides new insights into the reactions of cyanoarene-based PCâ¢â in photoredox-mediated reactions.
Current technological advances in the organic light-emitting diode panel design of foldable smartphones demand advanced adhesives with UV-blocking abilities, beyond their conventional roles of bonding objects and relieving deformation stress. However, optically clear adhesives (OCAs) with UV-blocking ability cannot be prepared using conventional UV-curing methods relying on a photoinitiator. Herein, a new acrylic resin that can be efficiently cured using visible light without oxygen removal is presented, which may be used to develop UV-blocking OCAs for use in current flexible displays. A novel photocatalyst and a specific combination of additives facilitate sufficiently rapid curing under visible light in the presence of UV-absorbers. Only a very small amount of the highly active photocatalyst is required to prepare UV-blocking OCA films with very high transparency in the visible region. Using this system, a UV-blocking OCA that nearly meets the specifications of an OCA used in commercialized foldable smartphones is realized. This technology can also be utilized in other applications that require highly efficient visible light curing, such as optically clear resins, dental resins, and 3D/4D-printable materials.
Since the pioneering discovery of a protein bound to poly(ethylene glycol), the utility of protein-polymer conjugates (PPCs) is rapidly expanding to currently emerging applications. Photoinduced energy/electron-transfer reversible addition-fragmentation chain-transfer (PET-RAFT) polymerization is a very promising method to prepare structurally well-defined PPCs, as it eliminates high-cost and time-consuming deoxygenation processes due to its oxygen tolerance. However, the oxygen-tolerance behavior of PET-RAFT polymerization is not well-investigated in aqueous environments, and thereby the preparation of PPCs using PET-RAFT polymerization needs a substantial amount of sacrificial reducing agents or inert-gas purging processes. Herein a novel water-soluble and biocompatible organic photocatalyst (PC) is reported, which enables visible-light-driven additive-free "grafting-from" polymerizations of a protein in ambient and aqueous environments. Interestingly, the developed PC shows unconventional "oxygen-acceleration" behavior for a variety of acrylic and acrylamide monomers in aqueous conditions without any additives, which are apparently distinct from previously reported systems. With such a PC, "grafting-from" polymerizations are successfully performed from protein in ambient buffer conditions under green light-emitting diode (LED) irradiation, which result in various PPCs that have neutral, anionic, cationic, and zwitterionic polyacrylates, and polyacrylamides. It is believed that this PC will be widely employed for a variety of photocatalysis processes in aqueous environments, including the living cell system.
Polymers , Water , Oxygen , Polymerization , Proteins
Owing to their excellent properties, such as transparency, resistance to oxidation, and high adhesivity, acrylic pressure-sensitive adhesives (PSAs) are widely used. Recently, solvent-free acrylic PSAs, which are typically prepared via photopolymerization, have attracted increasing attention because of the current strict environmental regulations. UV light is commonly used as an excitation source for photopolymerization, whereas visible light, which is safer for humans, is rarely utilized. In this study, we prepared solvent-free acrylic PSAs via visible light-driven photoredox-mediated radical polymerization. Three α-haloesters were used as additives to overcome critical shortcomings, such as the previously reported low film curing rate and poor transparency observed during additive-free photocatalytic polymerization. The film curing rate was greatly increased in the presence of α-haloesters, which lowered the photocatalyst loadings and, hence, improved the film transparency. These results confirmed that our method could be widely used to prepare general-purpose solvent-free PSAs-in particular, optically clear adhesives for electronics.
Light , Adhesives , Humans , Oxidation-Reduction , Photochemical Processes , Polymerization , Pressure
2D materials, such as graphene, exhibit great potential as functional materials for numerous novel applications due to their excellent properties. The grafting of conventional micropatterning techniques on new types of electronic devices is required to fully utilize the unique nature of graphene. However, the conventional lithography and polymer-supported transfer methods often induce the contamination and damage of the graphene surface due to polymer residues and harsh wet-transfer conditions. Herein, a novel strategy to obtain micropatterned graphene on polymer substrates using a direct curing process is demonstrated. Employing this method, entirely flexible, transparent, well-defined self-activated graphene sensor arrays, capable of gas discrimination without external heating, are fabricated on 4 in. wafer-scale substrates. Finite element method simulations show the potential of this patterning technique to maximize the performance of the sensor devices when the active channels of the 2D material are suspended and nanoscaled. This study contributes considerably to the development of flexible functional electronic devices based on 2D materials.
Soft magnetic materials have shown promise in diverse applications due to their fast response, remote actuation, and large penetration range for various conditions. Herein, a new soft magnetic composite material capable of reprogramming its magnetization profile without changing intrinsic magnetic properties of embedded magnetic particles or the molecular property of base material is reported. This composite contains magnetic microspheres in an elastomeric matrix, and the magnetic microspheres are composed of ferromagnetic microparticles encapsulated with oligomeric-PEG. By controlling the encapsulating polymer phase transition, the magnetization profiles of the magnetic composite can be rewritten by physically realigning the ferromagnetic particles. Diverse magnetic actuators with reprogrammable magnetization profiles are developed to demonstrate the complete reprogramming of complex magnetization profile.
The addition of chemical additives is considered as a promising approach for obtaining high-quality perovskite films under mild conditions, which is essential for both the efficiency and the stability of organic-inorganic hybrid perovskite solar cells (PeSCs). Although such additive engineering yields high-quality films, the inherent insulating property of the chemical additives prevents the efficient transport and extraction of charge carriers, thereby limiting the applicability of this approach. Here, it is shown that organic conjugated molecules having rhodanine moieties (i.e., SA-1 and SA-2) can be used as semiconducting chemical additives that simultaneously yield large-sized perovskite grains and improve the charge extraction. Using this strategy, a high power conversion efficiency of 20.3% as well as significantly improved long-term stability under humid air conditions is achieved. It is believed that this approach can provide a new pathway to designing chemical additives for further improving the efficiency and stability of PeSCs.
The highly sensitive optical detection of oxygen including dissolved oxygen (DO) is of great interest in various applications. We devised a novel room-temperature-phosphorescence (RTP)-based oxygen detection platform by constructing core-shell nanoparticles with water-soluble polymethyloxazoline shells and oxygen-permeable polystyrene cores crosslinked with metal-free purely organic phosphors. The resulting nanoparticles show a very high sensitivity for DO with a limit of detection (LOD) of 60â nm and can be readily used for oxygen quantification in aqueous environments as well as the gaseous phase.
Differentiation of solvents having similar physicochemical properties, such as ethanol and methanol, is an important issue of interest. However, without performing chemical analyses, discrimination between methanol and ethanol is highly challenging due to their similarity in chemical structure as well as properties. Here, we present a novel type of alcohol and water sensor based on the subtle differences in interaction among solvent analytes, fluorescent organic molecules, and a mesoporous silica gel substrate. A gradual change in the chemical structure of the fluorescent diketopyrrolopyrrole (DPP) derivatives alters their interaction with the substrate and solvent analyte, which creates a distinct intermolecular aggregation of the DPP derivatives on the silica gel substrate depending on the solvent environment and produces a change in the fluorescence color and intensity as a sensory signal. The devised sensor device, which is fabricated with simple drop-casting of the DPP derivative solutions onto a silica gel substrate, exhibited a completely reversible fluorescence signal change with large fluorescence signal contrast, which allows selective solvent detection by simple optical observation with the naked eye under UV light. Superior selectivity of the alcohol and water sensor system, which can clearly distinguish among ethanol, methanol, ethylene glycol, and water, is demonstrated.
Metal-free organic phosphors can be an attractive smart optical sensing materials since, in such compounds, intersystem crossing (ISC) and the phosphorescence process are placed in subtle competition with fluorescence, internal conversion (IC), and non-radiative decay pathways. Here, we report a unique environment-dependent multi-luminescence switching behavior of metal-free organic phosphorescent materials. Through combined photophysical measurements and computational electronic structure analysis, we systematically investigated how physicochemical properties of organic solvents affect the photophysical pathways of the metal-free organic phosphors. By rationally adapting the finding into phosphor-doped electrospun polymer fibers, we developed a new luminometric sensory platform and achieved selective detection of eight different common organic solvents. The presented finding provides new possibilities for metal-free organic phosphors to be a novel class of smart optical sensory materials.
