Synchronously Manipulating Absorption and Extinction Coefficient of Semiconducting Polymers via Precise Dual-Acceptor Engineering for NIR-II Excited Photothermal Theranostics

Integrating the ultralong excitation wavelength, high extinction coefficient, and prominent photothermal conversion ability into a single photothermal agent is an appealing yet significantly challenging task. Herein, a precise dual-acceptor engineering strategy is exploited for this attempt based on donor-acceptor (D-A) type semiconductor polymers by subtly regulating the molar proportions of the two employed electron acceptor moieties featuring different electronic affinity and π-conjugation degrees, and making full use of the active intramolecular motion-induced photothermal effect. The optimal polymer SP4 synchronously shows desirable second near-infrared (NIR-II) absorption, an extremely high extinction coefficient, and satisfactory photothermal conversion behavior. Consequently, the unprecedented performance of SP4 NPs on 1064 nm laser-excited photoacoustic imaging (PAI)-guided photothermal therapy (PTT) is demonstrated by the precise tumor diagnosis and complete tumor elimination.     

Direct Insertion Polymerization of Ionic Monomers: Rapid Production of Anion Exchange Membranes

The limited number of methods to directly polymerize ionic monomers currently hinders rapid diversification and production of ionic polymeric materials, namely anion exchange membranes (AEMs) which are essential components in emerging alkaline fuel cell and electrolyzer technologies. Herein, we report a direct coordination-insertion polymerization of cationic monomers, providing the first direct synthesis of aliphatic polymers with high ion incorporations and allowing facile access to a broad range of materials. We demonstrate the utility of this method by rapidly generating a library of solution processable ionic polymers for use as AEMs. We investigate these materials to study the influence of cation identity on hydroxide conductivity and stability. We found that AEMs with piperidinium cations exhibited the highest performance, with high alkaline stability, hydroxide conductivity of 87 mS cm⁻¹ at 80 °C, and a peak power density of 730 mW cm⁻² when integrated into a fuel cell device.     

Non-activated Esters as Reactive Handles in Direct Post-Polymerization Modification

Non-activated esters are prominently featured functional groups in polymer science, as ester functional monomers display great structural diversity and excellent compatibility with a wide range of polymerization mechanisms. Yet, their direct use as a reactive handle in post-polymerization modification has been typically avoided due to their low reactivity, which impairs the quantitative conversion typically desired in post-polymerization modification reactions. While activated ester approaches are a well-established alternative, the modification of non-activated esters remains a synthetic and economically valuable opportunity. In this review, we discuss past and recent efforts in the utilization of non-activated ester groups as a reactive handle to facilitate transesterification and aminolysis/amidation reactions, and the potential of the developed methodologies in the context of macromolecular engineering.     

An Efficient Direct Arylation Polycondensation via C−S Bond Cleavage

The direct arylation polycondensation (DArP) has become one of the most important methods to construct conjugated polymers (CPs). However, the homocoupling side-reactions of aryl halides and the low regioseletive reactivities of unfunctionalized aryls hinder the development of DArP. Here, an efficient Pd and Cu co-catalyzed DArP was developed via inert C−S bond cleavage of aryl thioethers, of which robustness was exemplified by over twenty conjugated polymers (CPs), including copolymers, homopolymers, and random polymers. The capture of oxidative addition intermediate together with experimental and theoretic results suggested the important role of palladium (Pd) and copper (Cu) co-catalysis with a bicyclic mechanism. The studies of NMR, molecular weights, trap densities, two-dimensional grazing-incidence wide-angle X-ray scattering (2D-GIWAXS), and the charge transport mobilities revealed that the homocoupling reactions were significantly suppressed with high regioselectivity of unfunctionalized aryls, suggesting this method is an excellent choice for synthesizing high performance CPs.     

Practical Synthesis of Dendritic Hyperbranched Polyacrylates and Their Topological Block Polymers by Organotellurium-Mediated Emulsion Polymerization in Water**

The practical synthesis of structurally controlled hyperbranched polymers (HBPs) by organotellurium-mediated radical polymerization (TERP) in water under emulsion conditions is reported. Copolymerization of vinyltelluride named evolmer, which induces controlled branch structure, and acrylates with TERP chain transfer agent (CTA) in water afforded HBPs having dendron structure. The molecular weight, dispersity, branch number, and branch length of the HBPs were controlled by changing the amount of CTA, evolmer, and acrylate monomers. HB-poly(butyl acrylate)s (HBPBAs) with up to the 8^th generation having an average of 255 branches were successfully synthesized. As the monomer conversion reached nearly quantitative and the obtained polymer particles were well dispersed in water, the method is highly suitable for synthesizing topological block polymers, block polymers consisting of different topologies. Thus, linear-block-HB, HB-block-linear, and HB-block-HB-PBAs with the controlled structure were successfully synthesized by adding the second monomer(s) to the macro-CTA. The intrinsic viscosity of the resulting homo- and topological block PBAs was systematically controlled by the degree of the branch, the branch length, and the topology. Therefore, the method opens the possibility of obtaining various HBPs with diverse branch structures and tuning the polymer properties by the polymer topology.     

An n-Type Polythiophene Derivative with Excellent Thermoelectric Performance

Typical n-type conjugated polymers are based on fused-ring electron-accepting building blocks. Herein, we report a non-fused-ring strategy to design n-type conjugated polymers, i.e. introducing electron-withdrawing imide or cyano groups to each thiophene unit of a non-fused-ring polythiophene backbone. The resulting polymer, n-PT1 , shows low LUMO/HOMO energy levels of −3.91 eV/−6.22 eV, high electron mobility of 0.39 cm² V⁻¹ s⁻¹ and high crystallinity in thin film. After n-doping, n-PT1 exhibits excellent thermoelectric performance with an electrical conductivity of 61.2 S cm⁻¹ and a power factor (PF) of 141.7 μW m⁻¹ K⁻². This PF is the highest value reported so far for n-type conjugated polymers and this is the first time for polythiophene derivatives to be used in n-type organic thermoelectrics. The excellent thermoelectric performance of n-PT1 is due to its superior tolerance to doping. This work indicates that polythiophene derivatives without fused rings are low-cost and high-performance n-type conjugated polymers.     

Rotaxane Formation of Multicyclic Polydimethylsiloxane in a Silicone Network: A Step toward Constructing “Macro-Rotaxanes” from High-Molecular-Weight Axle and Wheel Components

Rotaxanes consisting of a high-molecular-weight axle and wheel components (macro-rotaxanes) have high structural freedom, and are attractive for soft-material applications. However, their synthesis remains underexplored. Here, we investigated macro-rotaxane formation by the topological trapping of multicyclic polydimethylsiloxanes (mc-PDMSs) in silicone networks. mc-PDMS with different numbers of cyclic units and ring sizes was synthesized by cyclopolymerization of a α,ω-norbornenyl-functionalized PDMS. Silicone networks were prepared in the presence of 10–60 wt % mc-PDMS, and the trapping efficiency of mc-PDMS was determined. In contrast to monocyclic PDMS, mc-PDMSs with more cyclic units and larger ring sizes can be quantitatively trapped in the network as macro-rotaxanes. The damping performance of a 60 wt % mc-PDMS-blended silicone network was evaluated, revealing a higher tan δ value than the bare PDMS network. Thus, macro-rotaxanes are promising as non-leaching additives for network polymers.     

Photocatalysis as an Effective Tool for Upcycling Polymers into Value-Added Molecules

Shaping a sustainable future is closely tied to the development of advanced plastic recycling technologies. As global recycling rates remain low, the lion's share of post-consumer plastics is either incinerated or disposed of in landfills. This unbalanced plastic waste management not only poses severe environmental risks, but also entails an irrevocable loss of chemical resources that are embedded in synthetic polymers. To give plastic waste a new life, a series of photocatalytic methods has recently been reported that convert polymers directly into value-added organic molecules. These approaches operate at ambient temperature, show high reactivity/selectivity, and provide alternative reaction pathways as compared to thermal depolymerizations. This Minireview highlights the scientific breakthroughs in upcycling polymers through state-of-the-art photocatalysis under environmentally benign conditions.     

Modulating the Differentiation of Kinetically Controlled Supramolecular Polymerizations through the Alkyl Bridge Length

The synthesis and self-assembling features of N-annulated perylenebisimides (N-PBIs) 2 – 4 are reported and compared with the complex self-assembly of N-PBI 1 . The studies presented herein demonstrate that increasing the length of the alkyl spacer separating the central aromatic core of the dye and the peripheral side chains cancels the differentiation on the corresponding supramolecular polymerization. Thus, only 2 is able to form two different supramolecular polymorphs. The formation of kinetically trapped monomeric species is observed for all the N-PBIs 2 – 4 . These metastable species, constituted by intramolecularly H-bonded pseudocycles of 7, 8, 9, or 10 members for compounds 1 , 2 , 3 , and 4 , respectively, provoke kinetically controlled supramolecular polymerizations that can be accelerated by the addition of seeds. The results presented herein shed light on the intricate process of differentiation in self-assembly.     

Supramolecular Block Copolymers from Tricarboxamides. Biasing Co-assembly by the Incorporation of Pyridine Rings

The synthesis of a series of triangular-shaped tricarboxamides endowed with three picoline or nicotine units (compounds 2 and 3 , respectively) or just one nicotine unit (compound 4 ) is reported, and their self-assembling features investigated. The pyridine rings make compounds 2 – 4 electronically complementary with our previously reported oligo(phenylene ethynylene)tricarboxamides (OPE-TA) 1 to form supramolecular copolymers. C₃-symmetric tricarboxamide 2 forms highly stable intramolecular five-membered pseudocycles that impede its supramolecular polymerization into poly-2 and the co-assembly with 1 to yield copolymer poly-1-co-2 . On the other hand, C₃-symmetric tricarboxamide 3 readily forms poly-3 with great stability but unable to form helical supramolecular polymers despite the presence of the peripheral chiral side chains. The copolymer poly-1-co-3 can only be obtained by a previous complete disassembly of the constitutive homopolymers in CHCl₃. Helical poly-1-co-3 arises in a process involving the transfer of the helicity from racemic poly-1 to poly-3 , and the amplification of asymmetry from chiral poly-3 to poly-1 . Importantly, C_2v-symmetric 4 , endowed with only one nicotinamide moiety and three chiral side chains, self-assembles into a P-type helical supramolecular polymer ( poly-4 ) in a thermodynamically controlled cooperative process. The combination of poly-1 and poly-4 generates chiral supramolecular copolymer poly-1-co-4 , whose blocky microstructure has been investigated by applying the previously reported supramolecular copolymerization model.