Photocontrolled RAFT polymerization: past, present, and future.

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.

Tailoring the Degradation of Cyanoarene-Based Photocatalysts for Enhanced Visible-Light-Driven Halogen Atom Transfer.

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 the 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.

Characterization of the Reversible Intersystem Crossing Dynamics of Organic Photocatalysts Using Transient Absorption Spectroscopy and Time-Resolved Fluorescence Spectroscopy.

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).

Reprogrammable Ferromagnetic Domains for Reconfigurable Soft Magnetic Actuators.

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.

Visible-Light-Curable Solvent-Free Acrylic Pressure-Sensitive Adhesives via Photoredox-Mediated Radical Polymerization.

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.

Room-Temperature-Phosphorescence-Based Dissolved Oxygen Detection by Core-Shell Polymer Nanoparticles Containing Metal-Free Organic Phosphors.

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 60 nm and can be readily used for oxygen quantification in aqueous environments as well as the gaseous phase.

High thermal conductivity in amorphous polymer blends by engineered interchain interactions.

Thermal conductivity is an important property for polymers, as it often affects product reliability (for example, electronics packaging), functionality (for example, thermal interface materials) and/or manufacturing cost. However, polymer thermal conductivities primarily fall within a relatively narrow range (0.1-0.5 W m(-1) K(-1)) and are largely unexplored. Here, we show that a blend of two polymers with high miscibility and appropriately chosen linker structure can yield a dense and homogeneously distributed thermal network. A sharp increase in cross-plane thermal conductivity is observed under these conditions, reaching over 1.5 W m(-1) K(-1) in typical spin-cast polymer blend films of nanoscale thickness, which is approximately an order of magnitude larger than that of other amorphous polymers.

Tailoring intermolecular interactions for efficient room-temperature phosphorescence from purely organic materials in amorphous polymer matrices.

Herein we report a rational design strategy for tailoring intermolecular interactions to enhance room-temperature phosphorescence from purely organic materials in amorphous matrices at ambient conditions. The built-in strong halogen and hydrogen bonding between the newly developed phosphor G1 and the poly(vinyl alcohol) (PVA) matrix efficiently suppresses vibrational dissipation and thus enables bright room-temperature phosphorescence (RTP) with quantum yields reaching 24%. Furthermore, we found that modulation of the strength of halogen and hydrogen bonding in the G1-PVA system by water molecules produced unique reversible phosphorescence-to-fluorescence switching behavior. This unique system can be utilized as a ratiometric water sensor.

Highly efficient dual photoredox/copper catalyzed atom transfer radical polymerization achieved through mechanism-driven photocatalyst design.

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.

Biomass-Derived Optically Clear Adhesives for Foldable Displays.

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.

Ultraviolet Light Debondable Optically Clear Adhesives for Flexible Displays through Efficient Visible-Light Curing.

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.

Functional Thermoplastic Polyurethane Elastomers with α, ω-Hydroxyl End-Functionalized Polyacrylates.

Thermoplastic polyurethane (TPU) is an essential class of materials for demanding applications, from soft robotics and electronics to medical devices and batteries. However, traditional TPU development is primarily relied on specific soft segments, such as polyether, polyester, and polycarbonate polyols. Here, a novel method is introduced for developing TPU elastomers with enhanced performance and superior functionalities compared to conventional TPUs, achieved through the use of α,ω-hydroxyl end-functionalized polyacrylates. This approach involves a defect-free synthesis of α,ω-hydroxyl end-functionalized polyacrylates through visible-light-driven photoiniferter polymerization. By strategically blending these functionalized polyacrylates with conventional polyols, TPUs that exhibit exceptional toughness and notable self-healing capabilities, traits rarely found in existing TPUs are engineered. Furthermore, incorporating photo-crosslinkable acrylic monomers has enabled the creation of the first TPU with superior elastomeric properties and photopatterning capabilities. This approach paves the way for a new direction in polyurethane engineering, introducing a novel class of soft segments and unlocking the potential for a wide range of advanced applications.

Rational Design of Color-Pure Blue Organic Emitters by Poly-Heteroaromatic Omni-Delocalization.

Current research on organic light emitters which utilize multiple resonance-induced thermally activated delayed fluorescence (MR-TADF) materials is gaining significant interest because of the materials' ability to efficiently generate color-pure blue emission. However, the underlying reasons for high color purity remain unclear. It is shown here that these emitters share a common electronic basis, which is deduced from resonance structure considerations following Clar's rule, and which is termed as "poly-heteroaromatic omni-delocalization" (PHOD). The simple and clear design rules derived from the PHOD concept allow extending the known chemical space by new structural motifs. Based on PHOD, a set of novel high-efficiency color-pure emitters with brilliant deep-blue hue is specifically designed.

Visible-Light-Driven Rapid 3D Printing of Photoresponsive Resins for Optically Clear Multifunctional 3D Objects.

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.

Ultraviolet light blocking optically clear adhesives for foldable displays via highly efficient visible-light curing.

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.

Magnetically Actuated Trigger Transient Soft Actuators Comprising On-Demand Photo-Initiated and Thermo-Degradable Polypropylene Carbonate-Photo-Acid Generator.

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.

Formation and degradation of strongly reducing cyanoarene-based radical anions towards efficient radical anion-mediated photoredox catalysis.

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 (PC•‒) are still insufficiently understood. Herein, we therefore investigate the formation and degradation of cyanoarene-based PC•‒ under widely-used photoredox-mediated reaction conditions. By screening various cyanoarene-based PCs, we elucidate strategies to efficiently generate PC•‒ with adequate excited-state reduction potentials (Ered*) via supra-efficient generation of long-lived triplet excited states (T1). To thoroughly investigate the behavior of PC•‒ in actual photoredox-mediated reactions, a reductive dehalogenation is carried out as a model reaction and identified the dominant photodegradation pathways of the PC•‒. Dehalogenation and photodegradation of PC•‒ 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 PC•‒, we demonstrate that the efficient generation of highly reducing PC•‒ 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 PC•‒ in photoredox-mediated reactions.

Visible-Light-Curable Acrylic Resins toward UV-Light-Blocking Adhesives for Foldable Displays.

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.

Donor-Acceptor-Donor Triads with Flexible Spacers: Deciphering Complex Photophysics for Targeted Materials Design.

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.

A Water-Soluble Organic Photocatalyst Discovered for Highly Efficient Additive-Free Visible-Light-Driven Grafting of Polymers from Proteins at Ambient and Aqueous Environments.

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.