Photo-Deactivation Strategy for Switchable ATRP with the Assistance of Molecular Switches.

Light irradiation is an external stimulus, rapidly developed in switchable atom transfer radical polymerization (ATRP) via photo-activation methods in recent years. Herein, a photo-deactivation strategy is introduced to regulate ATRP with the assistance of photoswitchable hexaarylbiimidozole (HABI). Under visible light irradiation and in the presence of HABI, ATRP is greatly decelerated or quenched depending on the concentration of HABI. Interestingly, with visible light off, ATRP can proceed smoothly and follow a first-order kinetics. Moreover, photo-switchable ATRP alternatively with light off and on is demonstrated. Besides, the mechanism of photo-deactivation ATRP involving radical quenching is proposed in the presence of HABI.

Precision Sequence-Defined Polymers: From Sequencing to Biological Functions.

Precise sequence-defined polymers (SDPs) with uniform chain-to-chain structure including chain length, unit sequence, and end functionalities represent the pinnacle of sophistication in the realm of polymer science. For example, the absolute control over the unit sequence of SDPs allows for the bottom-up design of polymers with hierarchical microstructures and functions. Accompanied with the development of synthetic techniques towards precision SDPs, the decoding of SDP sequences and construction of advanced functions irreplaceable by other synthetic materials is of central importance. In this Minireview, we focus on recent advances in SDP sequencing techniques including tandem mass spectrometry (MS), chemically assisted primary MS, as well as other non-destructive sequencing methods such as nuclear magnetic resonance (NMR) spectroscopy, circular dichroism (CD), and nanopore sequencing. Additionally, we delve into the promising prospects of SDP functions in the area of cutting-edge biological research. Topics of exploration include gene delivery systems, the development of hybrid materials combining SDPs and nucleic acids, protein recognition and regulation, as well as the interplay between chirality and biological functions. A brief outlook towards the future directions of SDPs is also presented.

Heteroatom Substitution Strategy Modulates Thermodynamics Towards Chemically Recyclable Polyesters and Monomeric Unit Sequence by Temperature Switching.

In this paper, we proposed a heteroatom substitution strategy (HSS) in the δ-valerolactone (VL) system to modulate thermodynamics toward chemically recyclable polyesters. Three VL-based monomers containing different heteroatoms (M1 (N), M2 (S), and M3 (O)), instead of C-5 carbon, were designed and synthesized to verify our proposed HSS. All three monomers undergo organocatalytic living/controlled ROP and controllable depolymerization. Impressively, the resulting P(M1) achieved over 99 % monomer recovery under both mild solution depolymerization and high vacuum pyrolysis conditions without any side reactions, and the recycled monomers can be polymerized again forming new polymers. The systematic study of the relationship between heteroatom substitution and recyclability shows that introducing heteroatoms does change the thermodynamics of the monomers (ΔHp o, ΔSp o and Tc values), thereby adjusting the polymerizability and depolymerizability. DFT calculations found that the introduction of heteroatoms adjusts the ring strain by changing the angular strain of the monomers, and the order of their angular strain (M2>M1>M3) is consistent with the order of the experimentally obtained enthalpy change. Notably, the one-pot/one-step copolymerization of two of each of the three monomers enables the synthesis of sequence-controlled copolymers from gradient to random to block structures, by simply switching the copolymerization temperature.

Tuning the Mechanical Properties of 3D-printed Objects by the RAFT Process: From Chain-Growth to Step-Growth.

Photoinduced 3D printing based on the reversible addition-fragmentation chain transfer (RAFT) process has emerged as a robust method for creating diverse functional materials. However, achieving precise control over the mechanical properties of these printed objects remains a critical challenge for practical application. Here, we demonstrated a RAFT step-growth polymerization of a bifunctional xanthate and bifunctional vinyl acetate. Additionally, we demonstrated photoinduced 3D printing through RAFT step-growth polymerization with a tetrafunctional xanthate and a bifunctional vinyl acetate. By adjusting the molar ratio of the components in the printing resins, we finely tuned the polymerization mechanism from step-growth to chain-growth. This adjustment resulted in a remarkable range of tunable Young's moduli, ranging from 7.6 MPa to 997.1 MPa. Moreover, post-functionalization and polymer welding of the printed objects with varying mechanical properties opens up a promising way to produce tailor-made materials with specific and tunable properties.

Unraveling Dynamic Helicity Inversion and Chirality Transfer through the Synthesis of Discrete Azobenzene Oligomers by an Iterative Exponential Growth Strategy.

Unraveling the chirality transfer mechanism of polymer assemblies and controlling their handedness is beneficial for exploring the origin of hierarchical chirality and developing smart materials with desired chiroptical activities. However, polydisperse polymers often lead to an ambiguous or statistical evaluation of the structure-property relationship, and it remains unclear how the iterative number of repeating units function in the helicity inversion of polymer assemblies. Herein, we report the macroscopic helicity and dynamic manipulation of the chiroptical activity of supramolecular assemblies from discrete azobenzene-containing oligomers (azooligomers), together with the helicity inversion and morphological transition achieved solely by changing the iterative chain lengths. The corresponding assemblies also differ from their polydisperse counterparts in terms of thermodynamic properties, chiroptical activities, and morphological control.

Ultra-Fast Selenol-Yne Click (SYC) Reaction Enables Poly(selenoacetal) Covalent Adaptable Network Formation.

The emergence of covalent adaptable networks (CANs) based on dynamic covalent bonds (DCBs) presents a promising avenue for achieving resource recovery and utilization. In this study, we discovered a novel dynamic covalent bond called selenacetal, which is obtained through a double click reaction between selenol and activated alkynes. Density functional theory (DFT) calculations demonstrated that the ΔG for the formation of selenoacetals ranges from 12 to 18 kJ mol-1, suggesting its potential for dynamic reversibility. Dynamic exchange experiments involving small molecules and polymers provide substantial evidence supporting the dynamic exchange properties of selenoacetals. By utilizing this highly efficient click reaction, we successfully synthesized dynamic materials based on selenoacetal with remarkable reprocessing capabilities without any catalysts. These materials exhibit chemical recycling under alkaline conditions, wherein selenoacetal (SA) can decompose into active enone selenide (ES) and diselenides. Reintroducing selenol initiates a renewed reaction with the enone selenide, facilitating material recycling and yielding a newly developed dynamic material exhibiting both photo- and thermal responsiveness. The results underscore the potential of selenoacetal polymers in terms of recyclability and selective degradation, making them a valuable addition to conventional covalent adaptable networks.

Iodonium Initiators: Paving the Air-free Oxidation of Spiro-OMeTAD for Efficient and Stable Perovskite Solar Cells.

To date, perovskite solar cells (pero-SCs) with doped 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD) hole transporting layers (HTLs) have shown the highest recorded power conversion efficiencies (PCEs). However, their commercialization is still impeded by poor device stability owing to the hygroscopic lithium bis(trifluoromethanesulfonyl)imide and volatile 4-tert-butylpyridine dopants as well as time-consuming oxidation in air. In this study, we explored a series of single-component iodonium initiators with strong oxidability and different electron delocalization properties to precisely manipulate the oxidation states of Spiro-OMeTAD without air assistance, and the oxidation mechanism was clearly understood. Iodine (III) in the diphenyliodonium cation (IP+ ) can accept a single electron from Spiro-OMeTAD and forms Spiro-OMeTAD⋅+ owing to its strong oxidability. Moreover, because of the coordination of the strongly delocalized TFSI- with Spiro-OMeTAD⋅+ in a stable radical complex, the resulting hole mobility was 30 times higher than that of pristine Spiro-OMeTAD. In addition, the IP-TFSI initiator facilitated the growth of a homogeneous and pinhole-free Spiro-OMeTAD film. The pero-SCs based on this oxidizing HTL showed excellent efficiencies of 25.16 % (certified: 24.85 % for 0.062-cm2 ) and 20.71 % for a 15.03-cm2 module as well as remarkable overall stability.

Tailoring Hydrogen-Bonding Strategy for Sequence-Dependent and Thermo/pH Dual-Responsive Clusteroluminescence.

Rational design of monomer sequence for desired properties is challenging. This study investigates the effect of monomer distribution of double hydrophilic copolymers (DHCs) with electron-rich units on cluster triggered emission (CTE) capacity. By means of combining latent monomer strategy, reversible addition fragmentation chain transfer (RAFT) polymerization and selective hydrolysis technology, the random, pseudo di-block and the gradient DHCs consisting of pH-responsive polyacrylic acid (PAA) segments and thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) segments were successfully synthesized in a controlled manner. Moreover, the gradient DHCs showed a tremendously increased luminescent intensity due to the distinct hydrogen-bonding interaction compared to random and pseudo di-block DHCs. To the best of our knowledge, this is the first reported the direct correlation between luminescent intensity and sequence structure of non-conjugated polymer. Meanwhile, thermo and pH dual-responsive clusteroluminescence could be easily performed. This work demonstrates a novel and facile method to tailor the hydrogen-bonding for the stimuli-responsive light-emitting polymers.

Research Progress in Polypeptoids Prepared by Controlled Ring-Opening Polymerizations.

Polypeptoids, structural mimics of polypeptides, have attracted considerable attention due to their biocompatibility, proteolytic stability, thermal processability, good solubility, synthetic accessibility, and structural diversity. Polypeptoids have emerged as an interesting material in both polymer science and biological field. This review primarily discusses the research progress of polypeptoids prepared by controlled ring-opening polymerizations in the past decade, including synthetic strategies of monomers, polymerizations by different initiators, postfunctionalization, fundamental properties, crystallization-driven self-assembly, and potential biological applications.

Tailoring Polymerization Controllability and Dispersity Through a Photoswitchable Catalyst Strategy.

Modulating on-demand polymerization is a challenge in synthetic macromolecules. Herein, tailoring polymerization controllability and dispersity during single-electron transfer mediated living radical polymerization (SET-LRP) of methyl methacrylate (MMA) is achieved. Hexaarylbiimidazole (HABI) is employed as a photoswitchable catalyst, allowing reversible control of catalytic activity between an active and inactive state. In the presence of HABI and with the light on (active state), control SET-LRP of MMA follows first-order kinetics, resulting in polymers with a narrow molecular weight distribution. In contrast, polymerization responds to light and reverts to their original uncontrolled state with light off (inactive state). Therefore, repeatable resetting polymerization can be easily performed. The key to photomodulating dispersity is to use an efficient molecular switch to tailor the breadths of dispersity. Besides, the mechanism of HABI-mediated SET-LRP with switchable ability is proposed.

Fabrication and Decryption of a Microarray of Digital Dithiosuccinimide Oligomers.

Digital polymers with precisely arranged binary units provide an important option for information storage. This is especially true if the digital polymers are assembled in a device, as it would be of great benefit for data writing and reading in practice. Herein, inspired by the DNA microarray technique, the programmable information storing and reading on a mass spectrometry target plate is proposed. First, an array of 4-bit sequence-coded dithiosuccinimide oligomers is efficiently built through sequential thiol-maleimide Michael couplings with good sequence readability by tandem mass spectrometry (MS/MS). Then, toward engineering microarrays for information storage, a programmed robotic arm is specifically designed for precisely loading sequence-coded oligomers onto the target plate, and a decoding software is developed for efficient readout of the data from MS/MS sequencing. Notably, short sequence-coded oligomer chains can be used to write long strings of information, and extra error-correction codes are not required as usual due to the inherent concomitant fragmentation signals. Not only text but also bitimages can be automatically stored and decoded with excellent accuracy. This work provides a promising platform of digital polymers for programmable information storing and reading.

Stimuli-responsive polydopamine-based smart materials.

Stimuli responsiveness has long been a fascinating feature of smart material design. Polydopamine (PDA), a nature inspired polymeric pigment, exhibits excellent photo-responsive properties and has active surface functionality for loading various responsive motifs, making it a promising candidate for the construction of stimuli-responsive smart functional materials. PDA has long been considered as a robust coating material, but its responsive feature has rarely been emphasized in the past reviews. Herein, we present the first effort to summarize recent advances in the design strategies, responsive mechanisms, and diverse applications of stimuli-responsive PDA-based smart materials; the stimuli include light, pH, chemicals, temperature, humidity, electric fields, mechanical force, magnetic fields, and ultrasound. Moreover, the current trends, challenges, and future directions of stimuli-responsive PDA-based materials are also elaborated.

Precisely Encoding Geometric Features into Discrete Linear Polymer Chains for Robust Structural Engineering.

Molecular shape is an essential parameter that regulates the self-organization and recognition process, which has not yet been well appreciated and exploited in block polymers due to the lack of precise and efficient modulation methods. This work (i) develops a robust approach to break the intrinsic symmetry of linear polymers by introducing geometric features into otherwise homogeneous chains and (ii) quantitatively highlights the critical contribution of molecular geometry/architecture to the self-assembly behaviors. Iteratively connecting homologous monomers of different side chains according to pre-designed sequences generates discrete polymers with exact chemical structure, uniform chain length, and programmable side-chain gradient along the backbone, which transcribes into diverse shapes. The precise chemistry eliminates all the defects and heterogeneities, providing a delicate platform for fundamental inquiries into the role of molecular geometry. A rich collection of unconventional complex phases, including Frank-Kasper A15 and σ phases, as well as a dodecagonal quasicrystal phase, were captured in these rigorous single-component systems. The self-assembly behaviors are strikingly sensitive to subtle variations of geometry, such that simply migrating a few methylene units among the side chains would generate substantial differences in lattice size or phase stability, or even trigger a phase transition toward distinct structures. The phenomena can be rationalized with a geometric argument that nonuniform side chain distribution leads to conformational mismatch between two immiscible blocks, resulting in varied interfacial curvatures and distinct lattice symmetries. The profound contribution demonstrates that molecular geometry is an effective and robust parameter for structural engineering.

Polymerization-Induced Helicity Inversion Driven by Stacking Modes and Self-Assembly Pathway Differentiation.

Regulating the mutual stacking arrangements is of great interest for understanding the origin of chirality at different hierarchical levels in nature. Different from molecular level chirality, the control and manipulation of hierarchical chirality in polymer systems is limited to the use of external factors as the energetically demanding switching stimulus. Herein, the first self-assembly strategy of polymerization-induced helicity inversion (PIHI), in which the controlled packing and dynamic stereomutation of azobenzene (Azo) building blocks are realized by in situ polymerization without any external stimulus, is reported. A multiple helicity inversion and intriguing helix-helix transition of polymeric supramolecular nanofibers occurs during polymerization, which is collectively confirmed to be mediated by the transition between functionality-oriented π-π stacking, H-, and J-aggregation. The studies further reveal that helicity inversion proceeds through a delicate interplay of the thermodynamically and kinetically controlled, pathway-dependent interconversion process, which should provide new insight into the origin and handedness control of helical nanostructures with desired chirality.

2,5-Dimethylfuran/Acrylonitrile as Latent Monomer for Sequence-Controlled Copolymer and Sequence-Dependent Thermo-Responsivity.

Sequence control has attracted increasing attention for its ability of regulating polymer property and performance. Herein, the sequence-controlled polymer containing acrylonitrile (AN) is achieved by using 2,5-dimethylfuran/acrylonitrile adduct as a latent monomer. The temperature-dependent retro Diels-Alder reaction is engaged in controlling the release of AN during RAFT polymerization, that is, regulating the instant AN concentration via a non-invasive and in situ manner. Such control over the instant AN concentration and particularly the molar ratio of comonomer pair leads to the simultaneous change of monomer units in "living" polymeric chain, thus resulting in the sequence-controlled polymeric structures. By delicately manipulating the polymerization temperature, diverse sequence-on-demand structures of AN-containing copolymers, such as poly(AN/methyl methacrylate), poly(AN/styrene), poly(AN/butyl acrylate), poly(AN/N,N-dimethylacrylamide), and poly(AN/N-isopropylacrylamide) are created. Meanwhile, this study presents an initial attempt in tuning the thermal responsivity of poly(AN/N-isopropylacrylamide), which is closely correlated to the sequence of polymer structure. More importantly, the polymer with averagely distributed AN units results in the higher thermal sensitivity. Therefore, the synthetic strategy proposed in this work offers a promising platform for accessing the sequence-controlled copolymers containing AN structures, thus expanding the investigation on the relationship between the polymer structures and correlated properties.

Transfer, Amplification, Storage, and Complete Self-Recovery of Supramolecular Chirality in an Achiral Polymer System.

Supramolecular chirality and its complete self-recovery ability are highly mystical in nature and biological systems, which remains a major challenge today. Herein, we demonstrate that partially cross-linked azobenzene (Azo) units can be employed as the potential chiral trigger to fully heal the destroyed helical superstructure in achiral nematic polymer system. Combining the self-assembly of Azo units and terminal hydroxyl groups in polymer side chains allows the vapor-induced chiral nematic phase and covalent fixation of the superstructure via acetal reaction. The induced helical structure of Azo units can be stored by inter-chain cross-linking, even after removal of the chiral source. Most interestingly, the stored chiral information can trigger perfect chiral self-recovery (CSR) behavior after being destroyed by UV light, heat, and solvents. The results pave a new way for producing novel chiroptical materials with reversible chirality from achiral sources.

Controlling Polymer Molecular Weight Distribution through a Latent Mediator Strategy with Temporal Programming.

Polymer molecular weight distribution (MWD) is a key parameter of polymers. Here we present a robust method for controlling polymer MWD in controlled cationic polymerizations. A latent mediator strategy was designed and combined with temporal programming to regenerate mediators at different times during polymerization. Both the breadths and shapes of MWD curves were tuned easily by adjusting an external light source. Bimodal, trimodal, and tetramodal distributions were obtained, and the breadths could be varied from 1.06 to 2.09. Polymers with different MWDs prepared by this method had good chain end fidelity, which was demonstrated with successful chain-extension experiments. In addition, the introduction of temporal programming with a computer-controlled single chip for the light source opened an avenue for the use of artificial intelligence in polymer synthesis.

Using One Photoredox Catalyst to Simultaneously Mediate Two Different Polymerizations for Photo-Triggered Multi-Component Orthogonal Polymerizations.

The development of multi-component orthogonal polymerizations (MOPs) with simple procedure and high efficiency is crucial for rational polymer synthesis. In this work, photo-triggered Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization are first investigated, employing copper(II) thioxanthone carboxylate (Cu(TX)2 ) as photoredox catalyst and sunlight as stimuli. Then, the novel MOPs using one photoredox catalyst, Cu(TX)2 to simultaneously mediate two different photopolymerizations, are successfully realized in one-pot, where photo-induced electron transfer atom transfer radical polymerization and photo-activated CuAAC polymerization can effectively proceed in a one-pot and non-interfering fashion to afford predetermined copolymers with well-defined structure.

Selective and Rapid Light-Induced RAFT Single Unit Monomer Insertion in Aqueous Solution.

The photocatalyst Zn(II) meso-tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) is found to substantially accelerate visible-light-initiated (red, yellow, green light) single unit monomer insertion (SUMI) of N,N-dimethylacrylamide into the reversible addition-fragmentation chain transfer (RAFT) agent, 4-((((2-carboxyethyl)thio)carbonothioyl)thio)-4-cyanopentanoic acid (RAFT1 ), in aqueous solution. Thus, under irradiation with red (633 nm) or yellow (593 nm) light with 50 mpm (moles per million mole of monomer) ZnTPPS at 30 °C, the rate enhancement provided by photoinduced energy or electron transfer (PET) is ≈sevenfold over the rate of direct photoRAFT-SUMI (without catalyst), which corresponds to achieving full and selective reaction in hours versus days. Importantly, the selectivity, as judged by the absence of oligomers, is retained. Under green light at similar power, higher rates of SUMI are also observed. However, the degree of enhancement provided by PET-RAFT-SUMI over direct photoRAFT-SUMI as a function of catalyst concentration is less and some oligomers are formed.

Supramolecular Chirality in Azobenzene-Containing Polymer System: Traditional Postpolymerization Self-Assembly Versus In Situ Supramolecular Self-Assembly Strategy.

Recently, the design of novel supramolecular chiral materials has received a great deal of attention due to rapid developments in the fields of supramolecular chemistry and molecular self-assembly. Supramolecular chirality has been widely introduced to polymers containing photoresponsive azobenzene groups. On the one hand, supramolecular chiral structures of azobenzene-containing polymers (Azo-polymers) can be produced by nonsymmetric arrangement of Azo units through noncovalent interactions. On the other hand, the reversibility of the photoisomerization also allows for the control of the supramolecular organization of the Azo moieties within polymer structures. The construction of supramolecular chirality in Azo-polymeric self-assembled system is highly important for further developments in this field from both academic and practical points of view. The postpolymerization self-assembly strategy is one of the traditional strategies for mainly constructing supramolecular chirality in Azo-polymers. The in situ supramolecular self-assembly mediated by polymerization-induced self-assembly (PISA) is a facile one-pot approach for the construction of well-defined supramolecular chirality during polymerization process. In this review, we focus on a discussion of supramolecular chirality of Azo-polymer systems constructed by traditional postpolymerization self-assembly and PISA-mediated in situ supramolecular self-assembly. Furthermore, we will also summarize the basic concepts, seminal studies, recent trends, and perspectives in the constructions and applications of supramolecular chirality based on Azo-polymers with the hope to advance the development of supramolecular chirality in chemistry.