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Acenes are attractive as building blocks for low gap organic materials with applications, for example, in organic light emitting diodes, solar cells, bioimaging and diagnostics. Previously, we have shown that modification of dipyridylanthracene via B–N Lewis pair fusion (BDPA) strongly redshifts the emission, while facilitating self‐sensitized reactivity toward O2 to reversibly generate the corresponding endoperoxides. Herein, we report on the further expansion of the π‐system of BDPA to a vinyl‐substituted monomer, vinylene‐bridged dimer, and a polymer with an average of 20 chromophores. The extension of π‐conjugation results in largely reduced band gaps of 1.8 eV for the dimer and 1.7 eV for the polymer, the latter giving rise to NIR emission with a maximum at 731 nm and an appreciable quantum yield of 7 %. Electrochemical and computational studies reveal efficient delocalization of the lowest unoccupied molecular orbital (LUMO) along the pyridyl‐anthracene‐pyridyl axis, which results in effective electronic communication between BDPA units, selectively lowers the LUMO, and ultimately narrows the band gap. Time‐resolved emission and transient absorption (TA) measurements offer insights into the pertinent photophysical processes. Extension of π‐conjugation also slows down the self‐sensitized formation of endoperoxides, while significantly accelerating the thermal release of singlet oxygen to regenerate the parent acenes. [ABSTRACT FROM AUTHOR]

Conjugated polymers are emerging as competitive candidates for organic thermoelectrics (OTEs). However, to make the device truly pervasive, both p‐ and n‐type conjugated polymers are essential. Despite great efforts, no n‐type equivalents to the p‐type benchmark PEDOT:PSS exist to date mainly due to the low electrical conductivity (σ). Herein, a near‐amorphous n‐type conjugated polymer, namely pDFSe, is reported with high σ by achieving the synergy between charge transport and doping efficiency. The polymer pDFSe is synthesized based on an acceptor‐triad moiety of diketopyrrolopyrrole‐difluorobenzoselenadiazole‐diketopyrrolopyrrole (DFSe), which has the noncovalently‐fused‐ring structure to reinforce the backbone rigidity. Furthermore, an axisymmetric thiophene‐selenophene‐thiophene donor is introduced, which enables the formation of near‐amorphous microstructures. The above merits ensure good doping efficiency without scarifying efficient intrachain charge‐carrier transport. Thus, pDFSe‐based n‐type transistors exhibit high electron mobility up to 6.15 cm2 V−1 s−1, much higher than its reference polymer pDSe without the noncovalently‐fused‐ring structure (0.77 cm2 V−1 s−1). Further upon n‐doping, pDFSe demonstrates excellent σ of 62.6 S cm−1 and maximum power factor of 133.1 μW m−1 K−2, which are among the highest values reported for solution‐processed n‐type polymers. The results demonstrate the great potential of near‐amorphous n‐type conjugated polymers with noncovalently‐fused‐ring structure for the next‐generation OTEs. [ABSTRACT FROM AUTHOR]

The high level of lactate in tumor microenvironment not only promotes tumor development and metastasis, but also induces immune escape, which often leads to failures of various tumor therapy strategies. We here report a sono‐triggered cascade lactate depletion strategy by using semiconducting polymer nanoreactors (SPNLCu) for cancer cuproptosis‐immunotherapy. The SPNLCu mainly contain a semiconducting polymer as sonosensitizer, lactate oxidase (LOx) conjugated via a reactive oxygen species (ROS)‐cleavable linker and chelated Cu2+. Upon ultrasound (US) irradiation, the semiconducting polymer generates singlet oxygen (1O2) to cut ROS‐cleavable linker to allow the release of LOx that catalyzes lactate depletion to produce hydrogen peroxide (H2O2). The Cu2+ will be reduced to Cu+ in tumor microenvironment, which reacts with the produced H2O2 to obtain hydroxyl radical (⋅OH) that further improves LOx release via destroying ROS‐cleavable linkers. As such, sono‐triggered cascade release of LOx achieves effective lactate depletion, thus relieving immunosuppressive roles of lactate. Moreover, the toxic Cu+ induces cuproptosis to cause immunogenic cell death (ICD) for activating antitumor immunological effect. SPNLCu are used to treat both subcutaneous and deep‐tissue orthotopic pancreatic cancer with observably enhanced efficacy in restricting the tumor growths. This study thus provides a precise and effective lactate depletion tactic for cancer therapy. [ABSTRACT FROM AUTHOR]

Controlling the end‐groups of biocompatible polymers is crucial for enabling polymer‐based therapeutics and nanomedicine. Typically, end‐group diversification is a challenging and time‐consuming endeavor, especially for polymers prepared via ionic polymerization mechanisms with limited functional group tolerance. In this study, we present a facile end‐group diversification approach for poly(2‐oxazoline)s (POx), enabling quick and reliable production of heterotelechelic polymers to facilitate POxylation. The approach relies on the careful tuning of reaction parameters to establish differential reactivity of a pentafluorobenzyl initiator fragment and the living oxazolinium chain‐end, allowing the selective introduction of N‐, S‐, O‐nucleophiles via the termination of the polymerization, and a consecutive nucleophilic para‐fluoro substitution. The value of this approach for the accelerated development of nanomedicine is demonstrated through the synthesis of well‐defined lipid‐polymer conjugates and POx‐polypeptide block‐copolymers, which are well‐suited for drug and gene delivery. Furthermore, we investigated the application of a lipid‐POx conjugate for the formulation and delivery of mRNA‐loaded lipid nanoparticles for immunization against the SARS‐COV‐2 virus, underscoring the value of POx as a biocompatible polymer platform. [ABSTRACT FROM AUTHOR]

Conjugated polymers with tailorable composition and microarchitecture are propitious for modulating catalytic properties and deciphering inherent structure‐performance relationships. Herein, we report a facile linker engineering strategy to manipulate the electronic states of metallophthalocyanine conjugated polymers and uncover the vital role of organic linkers in facilitating electrocatalytic oxygen reduction reaction (ORR). Specifically, a set of cobalt phthalocyanine conjugated polymers (CoPc‐CPs) wrapped onto carbon nanotubes (denoted CNTs@CoPc‐CPs) are judiciously crafted via in situ assembling square‐planar cobalt tetraaminophthalocyanine (CoPc(NH2)4) with different linear aromatic dialdehyde‐based organic linkers in the presence of CNTs. Intriguingly, upon varying the electronic characteristic of organic linkers from terephthalaldehyde (TA) to 2,5‐thiophenedicarboxaldehyde (TDA) and then to thieno/thiophene‐2,5‐dicarboxaldehyde (bTDA), their corresponding CNTs@CoPc‐CPs exhibit gradually improved electrocatalytic ORR performance. More importantly, theoretical calculations reveal that the charge transfer from CoPc units to electron‐withdrawing linkers (i.e. TDA and bTDA) drives the delocalization of Co d‐orbital electrons, thereby downshifting the Co d‐band energy level. Accordingly, the active Co centers with more positive valence state exhibit optimized binding energy toward ORR‐relevant intermediates and thus a balanced adsorption/desorption pathway that endows significant enhancement in electrocatalytic ORR. This work demonstrates a molecular‐level engineering route for rationally designing efficient polymer catalysts and gaining insightful understanding of electrocatalytic mechanisms. [ABSTRACT FROM AUTHOR]

Open‐shell conjugated polymers with a high intrinsic conductivity and high‐spin ground state hold considerable promise for applications in organic electronics and spintronics. Herein, two novel acceptor‐acceptor (A–A) conjugated polymers based on a highly electron‐deficient quinoidal benzodifurandione unit have been developed, namely DPP‐BFDO‐Th and DPP‐BFDO. The incorporation of the quinoidal moiety into the polymers backbones enables deeply aligned lower‐lying lowest unoccupied molecular orbital (LUMO) levels of below −4.0 eV. Notably, DPP‐BFDO exhibits an exceptionally low LUMO (−4.63 eV) and a high‐spin ground state characterized by strong diradical characters. Moreover, a self‐doping through intermolecular charge‐transfer is observed for DPP‐BFDO, as evidenced by X‐ray photoelectron spectroscopy (XPS) studies. The high carrier concentration in combination with a planar and linear conjugated backbone yields a remarkable electrical conductivity (σ) of 1.04 S cm−1 in the "undoped" native form, ranking among the highest values reported for n‐type radical‐based conjugated polymers. When employed as an n‐type thermoelectric material, DPP‐BFDO achieves a power factor of 12.59 μW m−1 K−2. Furthermore, upon n‐doping, the σ could be improved to 65.68 S cm−1. This study underscores the great potential of electron‐deficient quinoidal units in constructing dopant‐free n‐type conductive polymers with a high‐spin ground state and exceptional intrinsic conductivity. [ABSTRACT FROM AUTHOR]

It remains challenging to comprehensively understand the packing models of conjugated polymers, in which side chains play extremely critical roles. The side chains are typically flexible and non‐conductive and are widely used to improve the polymer solubility in organic solutions. Herein, a buffer chain model is proposed to describe link between conjugated backbone and side chains for understanding the relationship of crystallization competition of conductive conjugated backbones and non‐conductive side chains. A longer buffer chain is beneficial for alleviating such crystallization competition and further promoting the spontaneous packing of conjugated backbones, resulting in enhanced charge transport properties. Our results provide a novel concept for designing conjugated polymers towards ordered organization and enhanced electronic properties and highlight the importance of balancing the competitive interactions between different parts of conjugated polymers. [ABSTRACT FROM AUTHOR]

Here, we build a tunable multipolar conjugated polymer framework platform via pore wall chemistry to probe the role of electronic structure engineering in improving the Li+ conduction by theoretical studies. Guided by theoretical prediction, we develop a new cyano‐vinylene‐linked multipolar polymer framework namely CNF‐COF, which can act as efficient ion sieves to modify solid polymer electrolytes to simultaneously tune Li+ migration and stable Li anodes for long‐lifespan all‐solid‐state (ASS) Li metal batteries at high rate. The dual‐decoration of cyano and fluorine groups in CNF‐COF favorably regulates electronic structure via multipolar donor‐acceptor electronic effects to afford proper energy band structure and abundant electron‐rich sites for enhanced oxidative stability, facilitated ion‐pair dissociation and suppressed anion movements. Thus, the CNF‐COF incorporation into poly (ethylene oxide) (PEO) electrolytes not only renders fast selective Li+ transport but also facilitates the Li dendrite suppression. Specifically, the constructed PEO composite electrolyte with an ultra‐low CNF‐COF content of only 0.5 wt % is endowed with a wide electrochemical window, a high ionic conductivity of 0.634 mS cm−1 at 60 °C and a large Li+ transference number of 0.81—remarkably outperforming CNF‐COF‐free counterparts (0.183 mS cm−1 and 0.22). As such, the Li symmetric cell delivers stable Li plating/stripping over 1400 h at 0.1 mA cm−2. Impressively, by coupling with LiFePO4 (LFP) cathodes, the assembled ASS Li battery under 60 °C allows for stable cycling over 2000 cycles at 1 C and over 1000 cycles even at 2 C with a large capacity retention of ~75 %, surpassing most reported ASS Li batteries using PEO‐based electrolytes. [ABSTRACT FROM AUTHOR]

Luminescence in the second near‐infrared (NIR‐II, 1,000–1,700 nm) window is beneficial especially for deep tissue imaging and optical sensors because of intrinsic high permeability through various media. Strong electron‐acceptors with low‐lying lowest unoccupied molecular orbital (LUMO) energy levels are a crucial unit for donor–acceptor (D–A) π‐conjugated polymers (CPs) with the NIR‐II emission property, however, limited kinds of molecular skeletons are still available. Herein, D–A CPs involving fluorinated boron‐fused azobenzene complexes (BAz) with enhanced electron‐accepting properties are reported. Combination of fluorination at the azobenzene ligand and trifluoromethylation at the boron can effectively lower the LUMO energy level down to −4.42 eV, which is much lower than those of conventional strong electron‐acceptors. The synthesized series of CPs showed excellent absorption/fluorescence property in solution over a wide NIR range including NIR‐II. Furthermore, owing to the inherent solid‐state emissive property of the BAz skeleton, obvious NIR‐II fluorescence from the film (up to λFL=1213 nm) and the nanoparticle in water (λFL=1036 nm, brightness=up to 29 cm−1 M−1) were observed, proposing that our materials are applicable for developing next‐generation of NIR‐II luminescent materials. [ABSTRACT FROM AUTHOR]

Optically active π‐conjugated polymers (OACPs) have garnered increasing research interest for their resemblance to biological helices and intriguing chirality‐related functions. Traditional methods for synthesizing involve decorating achiral conjugated polymer architectures with enantiopure side substituents through complex organic synthesis. Here, we report a new approach: the templated synthesis of unsubstituted OACPs via supramolecularly confined polymerizations of achiral monomers within nanopores of 2D or 3D chiral covalent organic frameworks (CCOFs). We show that the chiral π‐rich nanospaces facilitate the in situ enantiospecific polymerization and self‐propagation, akin to nonenzymatic polymerase chain reaction (PCR) system, resulting in chiral imprinting. The stacked polymer chains are kinetically inert enough to memorize the chiral information after liberating from CCOFs, and even after treatment at temperature up to 200 °C. The isolated OACPs demonstrate robust enantiodiscrimination, achieving up to 85 % ee in separating racemic amino acids. This underscores the potential of utilizing CCOFs as templates for supramolecularly imprinting optical activity into CPs, paving the way for synthetic evolution and advanced functional exploration of OACPs. [ABSTRACT FROM AUTHOR]

All‐polymer solar cells (all‐PSCs) have been regarded as one of the most promising candidates for commercial applications owing to their outstanding advantages such as mechanical flexibility, light weight and stable film morphology. However, compared to large amount of new‐emerging excellent polymer acceptors, the development of high‐performance polymer donor lags behind. Herein, a new D‐π‐A type polymer donor, namely QQ1, was developed based on dithienoquinoxalineimide (DTQI) as the A unit, benzodithiophene with thiophene‐conjugated side chains (BDTT) as the D unit, and alkyl‐thiophene as the π‐bridge, respectively. QQ1 not only possesses a strong dipole moment, but also shows a wide band gap of 1.80 eV and a deep HOMO energy level of −5.47 eV, even without halogen substituents that are commonly indispensable for high‐performance polymer donors. When blended with a classic polymer acceptor PY‐IT, the QQ1‐based all‐PSC delivers an outstanding PCE of 18.81 %. After the introduction of F‐BTA3 as the third component, a record PCE of 19.20 % was obtained, the highest value reported so far for all‐PSCs. The impressive photovoltaic performance originates from broad absorption range, reduced energy loss, and compact π–π stacking. These results provide new insight in the rational design of novel nonhalogenated polymer donors for further development of all‐PSCs. [ABSTRACT FROM AUTHOR]

Conjugated polymers (CPs) with low crystallinity are promising candidates for application in organic thermoelectrics (OTEs), particularly in flexible devices, because the disordered structures of these CPs can effectively accommodate dopants and ensure robust resistance to bending. However, n‐doped CPs usually exhibit poor thermoelectric performance, which hinders the development of high‐performance thermoelectric generators. Herein, we report an n‐type CP (ThDPP‐CNBTz) comprising two acceptor units: a thiophene‐flanked diketopyrrolopyrrole and a cyano‐functionalized benzothiadiazole. ThDPP‐CNBTz shows a low LUMO energy level of below −4.20 eV and features low crystallinity, enabling high doping efficiency. Moreover, the dual‐acceptor design enhances polaron delocalization, resulting in good thermoelectric performance. After n‐doping, ThDPP‐CNBTz exhibits an average electrical conductivity (σ) of 50.6 S cm−1 and a maximum power factor (PF) of 126.8 μW m−1 K−2, which is among the highest values reported for solution‐processed n‐type CPs to date. Additionally, a solution‐processed flexible OTE device based on doped ThDPP‐CNBTz exhibits a maximum PF of 70 μW m−1 K−2; the flexible device also shows remarkable resistance to bending strain, with only a marginal change in σ after 600 bending cycles. The findings presented in this work will advance the development of n‐type CPs for OTE devices, and flexible devices in particular. [ABSTRACT FROM AUTHOR]

Conjugated coordination polymers (c‐CPs) are unique organic–inorganic hybrid semiconductors with intrinsically high electrical conductivity and excellent charge carrier mobility. However, it remains a challenge in tailoring electronic structures, due to the lack of clear guidelines. Here, we develop a strategy wherein controlling the redox state of hydroquinone/benzoquinone (HQ/BQ) ligands allows for the modulation of the electronic structure of c‐CPs while maintaining the structural topology. The redox‐state control is achieved by reacting the ligand TTHQ (TTHQ=1,2,4,5‐tetrathiolhydroquinone) with silver acetate and silver nitrate, yielding Ag4TTHQ and Ag4TTBQ (TTBQ=1,2,4,5‐tetrathiolbenzoquinone), respectively. In spite of sharing the same topology consisting of a two‐dimensional Ag−S network and HQ/BQ layer, they exhibit different band gaps (1.5 eV for Ag4TTHQ and 0.5 eV for Ag4TTBQ) and conductivities (0.4 S/cm for Ag4TTHQ and 10 S/cm for Ag4TTBQ). DFT calculations reveal that these differences arise from the ligand oxidation state inhibiting energy band formation near the Fermi level in Ag4TTHQ. Consequently, Ag4TTHQ displays a high Seebeck coefficient of 330 μV/K and a power factor of 10 μW/m ⋅ K2, surpassing Ag4TTBQ and the other reported silver‐based c‐CPs. Furthermore, terahertz spectroscopy demonstrates high charge mobilities exceeding 130 cm2/V ⋅ s in both Ag4TTHQ and Ag4TTBQ. [ABSTRACT FROM AUTHOR]

High ambipolar mobility emissive conjugated polymers (HAME‐CPs) are perfect candidates for organic optoelectronic devices, such as polymer light emitting transistors. However, due to intrinsic trade‐off relationship between high ambipolar mobility and strong solid‐state luminescence, the development of HAME‐CPs suffers from high structural and synthetic complexity. Herein, a universal design principle and simple synthetic approach for HAME‐CPs are developed. A series of simple non‐fused polymers composed of charge transfer units, π bridges and emissive units are synthesized via a two‐step microwave assisted C−H arylation and direct arylation polymerization protocol with high total yields up to 61 %. The synthetic protocol is verified valid among 7 monomers and 8 polymers. Most importantly, all 8 conjugated polymers have strong solid‐state emission with high photoluminescence quantum yields up to 24 %. Furthermore, 4 polymers exhibit high ambipolar field effect mobility up to 10−2 cm2 V−1 s−1, and can be used in multifunctional optoelectronic devices. This work opens a new avenue for developing HAME‐CPs by efficient synthesis and rational design. [ABSTRACT FROM AUTHOR]

High‐performing n‐type polymers are crucial for the advance of organic electronics field, however strong electron‐deficient building blocks with optimized physicochemical properties for constructing them are still limited. The imide‐functionalized polycyclic aromatic hydrocarbons (PAHs) with extended π‐conjugated framework, high electron deficiency and good solubility serve as promising candidates for developing high‐performance n‐type polymers. Among the PAHs, phenanthrene (PhA) features a well‐delocalized aromatic π‐system with multiple modifiable active sites. However, the PhA‐based imides are seldom studied, mainly attributed to the synthetic challenge. Herein, we report two functionalized PhAs, CPOI and CPCNI, by simultaneously incorporating imide with carbonyl or dicyanomethylene onto PhA. Notably, the dicyanomethylene‐modified CPCNI exhibits a well stabilized LUMO energy level (−3.84 eV), attributed to the synergetic inductive effect from imide and cyano groups. Subsequently, based on CPOI and CPCNI, two polymers PCPOI‐Tz and PCPCNI‐Tz were developed. Applied to organic thin‐film transistors, owing to the strong electron‐deficiency of CPCNI, polymer PCPCNI‐Tz shows an improved electron mobility and largely decreased threshold voltage compared with PCPOI‐Tz. This work affords two structurally novel electron‐deficient building blocks and highlights the effectiveness of dual functionalization of PhAs with strong electron‐withdrawing groups for devising n‐type polymers. [ABSTRACT FROM AUTHOR]

Chemical modifications of enzymes excel in the realm of enzyme engineering due to its directness, robustness, and efficiency; however, challenges persist in devising versatile and effective strategies. In this study, we introduce a supramolecular modification methodology that amalgamates a supramolecular polymer with Candida antarctica lipase B (CalB) to create supramolecular enzymes (SupEnzyme). This approach features the straightforward preparation of a supramolecular amphiphilic polymer (β‐CD@SMA), which was subsequently conjugated to the enzyme, resulting in a SupEnzyme capable of self‐assembly into supramolecular nanoparticles. The resulting SupEnzyme nanoparticles can form micron‐scale supramolecular aggregates through supramolecular and electrostatic interactions with guest entities, thus enhancing catalyst recycling. Remarkably, these aggregates maintain 80 % activity after seven cycles, outperforming Novozym 435. Additionally, they can effectively initiate photobiocatalytic cascade reactions using guest photocatalysts. As a consequence, our SupEnzyme methodology exhibits noteworthy adaptability in enzyme modification, presenting a versatile platform for various polymer, enzyme, and biocompatible catalyst pairings, with potential applications in the fields of chemistry and biology. [ABSTRACT FROM AUTHOR]

Developing artificial enzymes based on organic molecules or polymers for reactive oxygen species (ROS)‐related catalysis has broad applicability. Herein, inspired by porphyrin‐based heme mimics, we report the synthesis of polyphthalocyanine‐based conjugated polymers (Fe‐PPc‐AE) as a new porphyrin‐evolving structure to serve as efficient and versatile artificial enzymes for augmented reactive oxygen catalysis. Owing to the structural advantages, such as enhanced π‐conjugation networks and π‐electron delocalization, promoted electron transfer, and unique Fe−N coordination centers, Fe‐PPc‐AE showed more efficient ROS‐production activity in terms of Vmax and turnover numbers as compared with porphyrin‐based conjugated polymers (Fe‐PPor‐AE), which also surpassed reported state‐of‐the‐art artificial enzymes in their activity. More interestingly, by changing the reaction medium and substrates, Fe‐PPc‐AE also revealed significantly improved activity and environmental adaptivity in many other ROS‐related biocatalytic processes, validating the potential of Fe‐PPc‐AE to replace conventional (poly)porphyrin‐based heme mimics for ROS‐related catalysis, biosensors, or biotherapeutics. It is suggested that this study will offer essential guidance for designing artificial enzymes based on organic molecules or polymers. [ABSTRACT FROM AUTHOR]

It is highly challenging to reproducibly prepare semiconducting polymers with targeted molecular weight tailored for next‐generation photovoltaic applications. Once such an easily accessible methodology is established, which can not only contribute to overcome the current limitation of the statistically determined nature of semiconducting polymers, but also facilitate rapid incorporation into the broad synthetic chemists' toolbox. Here, we describe a simple yet robust ultrasonication‐assisted Stille polymerization for accessing semiconducting polymers with high‐precision tailored molecular weights (from low to ultrahigh molecular weight ranges) while mitigating their interbatch variations. We propose that ultrasound‐induced simultaneous physical and chemical events enable precise control of the semiconducting polymers' molecular weights with high reproducibility to satisfy all the optical/electrical and morphological demands of diverse types of high‐performance semiconducting polymer‐based devices; as demonstrated in in‐depth experimental screenings in applications of both organic and perovskite photovoltaics. We believe that this methodology provides a fast development of new and existing semiconducting polymers with the highest‐level performances possible on various photovoltaic devices. [ABSTRACT FROM AUTHOR]

Organic electrode materials are promising for next‐generation energy storage materials due to their environmental friendliness and sustainable renewability. However, problems such as their high solubility in electrolytes and low intrinsic conductivity have always plagued their further application. Polymerization to form conjugated organic polymers can not only inhibit the dissolution of organic electrodes in the electrolyte, but also enhance the intrinsic conductivity of organic molecules. Herein, we synthesized a new conjugated organic polymer (COPs) COP500‐CuT2TP (poly [5,10,15,20‐tetra(2,2′‐bithiophen‐5‐yl) porphyrinato] copper (II)) by electrochemical polymerization method. Due to the self‐exfoliation behavior, the porphyrin cathode exhibited a reversible discharge capacity of 420 mAh g−1, and a high specific energy of 900 Wh Kg−1 with a first coulombic efficiency of 96 % at 100 mA g−1. Excellent cycling stability up to 8000 cycles without capacity loss was achieved even at a high current density of 5 A g−1. This highly conjugated structure promotes COP500‐CuT2TP combined high energy density, high power density, and good cycling stability, which would open new opportunity for the designable and versatile organic electrodes for electrochemical energy storage. [ABSTRACT FROM AUTHOR]

The manufacture of nitric acid (HNO3) consumes large amounts of energy and causes serious environmental pollution. Electrochemical synthesis is regarded as a key way to eliminate carbon emissions from the chemicals industry. The selective electrosynthesis of HNO3 from nitrogen was achieved by controllable assembly of cobalt metal on graphdiyne surface using a powerful tool of electrochemistry at ambient conditions. As an advanced material, graphdiyne (GDY) has a large conjugated structure on its surface and is rich in sp‐C triple bond skeleton, which can achieve strong interaction with metal atoms, resulting in incomplete charge transfer between graphdiyne and cobalt atoms. The experimental and theoretical calculation results show that the highly oxidized cobalt on graphdiyne (HOCo/GDY) can selectively and efficiently activate and convert the nitrogen into the key intermediate *NO, which promotes the efficient overall conversion performance of nitrogen to nitric acid. Thus, the highest nitric acid yield (192.0 μg h−1 mg−1) and Faradaic efficiency (21.5 %) were achieved at low potentials. [ABSTRACT FROM AUTHOR]

Conjugated polymers that can efficiently transport both ionic and electronic charges have broad applications in next‐generation optoelectronic, bioelectronic, and energy storage devices. To date, almost all the conjugated polymers have hydrophobic backbones, which impedes efficient ion diffusion/transport in aqueous media. Here, we design and synthesize a novel hydrophilic polymer building block, 4a‐azonia‐naphthalene (AN), drawing inspiration from biological systems. Because of the strong electron‐withdrawing ability of AN, the AN‐based polymers show typical n‐type charge transport behaviors. We find that cationic aromatics exhibit strong cation‐π interactions, leading to smaller π–π stacking distance, interesting ion diffusion behavior, and good morphology stability. Additionally, AN enhances the hydrophilicity and ionic‐electronic coupling of the polymer, which can help to improve ion diffusion/injection speed, and operational stability of organic electrochemical transistors (OECTs). The integration of cationic building blocks will undoubtedly enrich the material library for high‐performance n‐type conjugated polymers. [ABSTRACT FROM AUTHOR]

Organic electrode materials have attracted a lot interest in batteries in recent years. However, most of them still suffer from low performance such as low electrode potential, slow reaction kinetics, and short cycle life. In this work, we report a strategy of fabricating donor–acceptor (D–A) conjugated polymers for facilitating the charge transfer and therefore accelerating the reaction kinetics by using the copolymer (p‐TTPZ) of dihydrophenazine (PZ) and thianthrene (TT) as a proof‐of‐concept. The D–A conjugated polymer as p‐type cathode could store anions and exhibited high discharge voltages (two plateaus at 3.82 V, 3.16 V respectively), a reversible capacity of 152 mAh g−1 at 0.1 A g−1, excellent rate performance with a high capacity of 124.2 mAh g−1 at 10 A g−1 (≈50 C) and remarkable cyclability. The performance, especially the rate capability was much higher than that of its counterpart homopolymers without D–A structure. As a result, the p‐TTPZ//graphite full cells showed a high output voltage (3.26 V), a discharge specific capacity of 139.1 mAh g−1 at 0.05 A g−1 and excellent rate performance. This work provides a novel strategy for developing high performance organic electrode materials through molecular design and will pave a way towards high energy density organic batteries. [ABSTRACT FROM AUTHOR]

Highly efficient perovskite solar cells typically rely on spiro‐OMeTAD as a hole transporter, achieving a 25.7 % efficiency record. However, these cells are susceptible to harsh 85 °C conditions. Here, we present a peri‐xanthenoxanthene‐based semiconducting homopolymer (p‐TNI2) with matched energy levels and a high molecular weight, synthesized nearly quantitatively through facile oxidative polymerization. Compared to established materials, p‐TNI2 excels in hole mobility, morphology, modulus, and waterproofing. Implementing p‐TNI2 as the hole transport layer results in n‐i‐p perovskite solar cells with an initial average efficiency of 24.6 %, rivaling 24.4 % for the spiro‐OMeTAD control cells under identical conditions. Furthermore, the p‐TNI2‐based cells exhibit enhanced thermostability at 85 °C and operational robustness. [ABSTRACT FROM AUTHOR]

The conjugated organic semiconductor spacers have drawn wide attention in two‐dimensional (2D) perovskites and formamidinium (FA) has been widely used as A‐site cation in high‐performance 3D perovskite solar cells (PSCs). However, the FA‐based semiconductor spacers have rarely been investigated in 2D Ruddlesden‐Popper (RP) perovskites. Here, we developed two FA‐based spacers containing thieno[3,2‐b]thiophene (TT) and 2,2′‐bithiophene (BT) units, namely TTFA and BTFA, respectively, for 2D RP PSCs. The nucleation and crystallization kinetics of TTFA‐Pb and BTFA‐Pb from sol‐gel to film were investigated using in situ optical microscopy and in situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) measurements. It is found that the TTFA spacer could reduce the energy barrier of nucleation and induces crystal vertical orientation of 2D perovskite by forming larger clusters in precursor solution, resulting in much improved film quality. Benefiting from the enlarged crystal grains, reduced exciton binding energy, and decreased electron‐phonon coupling coefficient, the photovoltaic device based on (TTFA)2MAn−1PbnI3n+1 (n=5) achieved a champion efficiency of 19.41 %, which is a record for 2D RP PSCs with FA‐based spacers. Our work provides deep understanding of the nucleation and crystallization process of 2D RP perovskite films and highlights the great potential of FA‐based semiconductor spacers in highly efficient 2D PSCs. [ABSTRACT FROM AUTHOR]

In contrast to edge‐on and face‐on orientations, end‐on uniaxial conjugated polymers have the theoretical possibility of providing a macroscopic crystalline film. However, their fabrication is insurmountable due to sluggishly thermodynamic equilibrium states. Herein, we report the programmatic pathway to fabricate nanoarchitectonics on end‐on uniaxial conjugated metallopolymers by surface‐initiated simultaneous electrosynthesis and assembly. Self‐assembled monolayer (SAM) with bottom‐up oriented electroactive molecules as a temple allows orientation, stacking, and reactive addition of monomers triggered by switching alternative redox reactions as well as crystallization of small molecules. Repeating the same reaction can repair the unreactive site on the SAM and dynamically and statistically ensure maximum iterative coverage with ideal linear coefficients between optical or electrical responses and iterative times. The resulting nanoarchitectonics on uniaxially assembled end‐on polymers over centimeter‐sized areas have a subnanometer‐uniform morphology and exhibit ultrahigh modulus as well as an inorganic indium tin oxides and the highest conductance among conjugated molecular monolayers. Their memristive devices provide quantitative electrical and optical responses as a function of molecular length, bias, and iterative junctions. Precise processing of nanoarchitectonics as an electrically assisted assembly or printing technique can present sophisticated optoelectric functions and dimensional batch‐to‐batch consistency for micro‐sized organic materials and electronics. [ABSTRACT FROM AUTHOR]

Photocatalysts capable of harvesting a broad range of the solar spectrum are essential for sustainable chemical transformations and environmental remediation. Herein, we have integrated NIR‐absorbing upconversion nanoparticles (UCNP) with UV‐Vis absorbing conjugated porous organic polymer (POP) through the in situ multicomponent C−C coupling to fabricate a UC−POP nanocomposite. The light‐harvesting ability of UC−POP is further augmented by loading plasmonic gold nanoparticles (AuNP) into UC−POP. A three‐times enhancement in the upconversion luminescence is observed upon the incorporation of AuNP in UC−POP, subsequently boosting the photocatalytic activity of UC−POP−Au. The spectroscopic and photoelectrochemical investigations infer the enhanced photocatalytic oxidation of thioethers, including mustard gas simulant by UC−POP−Au compared to POP and UC−POP due to the facile electron‐hole pair generation, suppressed exciton recombination, and efficient charge carrier migration. Thus, the unique design strategy of combining plasmonic and upconversion nanoparticles with a conjugated porous organic polymer opens up new vistas towards artificial light harvesting. [ABSTRACT FROM AUTHOR]

Photodetectors are critical components in intelligent optoelectronic systems, and photomultiplication‐capable devices are essential for detecting weak optical signals. Despite significant advances, developing photomultiplication‐type organic photodetectors with high gain and low noise current simultaneously remains challenging. In this work, a new conjugated polymer PDN with singlet open‐shell ground state is introduced in active layers for electron capture, and the corresponding PDN‐based photodetectors exhibited an enhanced photoelectric gain and decreased dark current density at a low forward bias. At 1.5 V, the PDN‐based ternary photodetector has the external quantum efficiency (EQE) up to 2552.3 % and the specific detectivity of 1.4×1014 Jones at 710 nm calculated by the measured noise current, with the gain 22 times higher than that of the control group. This study provides an approach for exploiting polymers with singlet open‐shell ground state to enhance the gain of organic photodetectors. [ABSTRACT FROM AUTHOR]

The ubiquitous presence of per‐ and polyfluoroalkyl substances (PFAS) in aqueous environments has aroused societal concern. Nonetheless, effective sensing technologies for continuous monitoring of PFAS within water distribution infrastructures currently do not exist. Herein, we describe a ratiometric sensing approach to selectively detect aqueous perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) at concentrations of μg ⋅ L−1. Our method relies on the excitonic transport in a highly fluorinated poly(p‐phenylene ethynylene) to amplify a ratiometric emission signal modulated by an embedded fluorinated squaraine dye. The electronic coupling between the polymer and dye occurs through overlap of π‐orbitals and is designed such that energy transfer is dominated by an electron‐exchange (Dexter) mechanism. Exposure to aqueous solutions of PFAS perturbs the orbital interactions between the squaraine dye and the polymer backbone, thereby diminishing the efficiency of the energy transfer and producing a "polymer‐ON/dye‐OFF" response. These polymer/dye combinations were evaluated in spin‐coated films and polymer nanoparticles and were able to selectively detect PFAS at concentrations of ca. 150 ppb and ca. 50 ppb, respectively. Both polymer films and nanoparticles are not affected by the type of water, and similar responses to PFAS were found in milliQ and well water. [ABSTRACT FROM AUTHOR]

Nitrogen‐coordinated iron (Fe−N4) materials represent the most promising non‐noble electrocatalysts for the cathodic oxygen reduction reaction (ORR) of fuel cells. However, molecular‐level structure design of Fe−N4 electrocatalyst remains a great challenge. In this study, we develop a novel Fe−N4 conjugated organic polymer (COP) electrocatalyst, which allows for precise design of the Fe−N4 structure, leading to unprecedented ORR performance. At the molecular level, we have successfully organized spatially proximate iron‐pyrrole/pyrazine (FePr/Pz) pairs into fully conjugated polymer networks, which in turn endows FePr sites with firmly covalent‐bonded matrix, strong d‐π electron coupling and highly dense distribution. The resulting pyrazine‐linked iron‐coordinated tetrapyrrole (Pz−FeTPr) COP electrocatalyst exhibits superior performance compared to most ORR electrocatalysts, with a half‐wave potential of 0.933 V and negligible activity decay after 40,000 cycles. When used as the cathode electrocatalyst in a hydroxide exchange membrane fuel cell, the Pz−FeTPr COP achieves a peak power density of ≈210 mW cm−2. We anticipate the COP based Fe−N4 catalyst design could be an effective strategy to develop high‐performance catalyst for facilitating the progress of fuel cells. [ABSTRACT FROM AUTHOR]

Protein‐polymer conjugates have significant potential in pharmaceutical and biomedical applications. To enable their widespread use, robust conjugation techniques are crucial. This study introduces a photo‐initiated reversible addition‐fragmentation chain‐transfer (Photo‐RAFT) polymerization system that exhibits excellent oxygen tolerance. This system allows for the synthesis of protein‐polymer conjugates with high bioactivity under mild and aerobic conditions. Three photocatalytic systems utilizing Eosin Y (EY) as the photocatalyst with two different cocatalysts (ascorbic acid and triethanolamine) were investigated, each generating distinct reactive oxygen species (ROS) such as singlet oxygen, superoxide, hydrogen peroxide, and hydroxyl radicals. The impact of these ROS on three model proteins (lysozyme, albumin, and myoglobin) was evaluated, demonstrating varying bioactivities based on the ROS produced. The EY/TEOA system was identified as the optimal photo‐RAFT initiating system, enabling the preparation of protein‐polymer conjugates under aerobic conditions while maintaining high protein enzymatic activity. To showcase the potential of this approach, lysozyme‐poly(dimethylaminoethyl acrylate) conjugates were successfully prepared and exhibited enhanced antimicrobial property against Gram‐positive and Gram‐negative bacteria. [ABSTRACT FROM AUTHOR]

The incorporation of insulating polymers into conjugated polymers has been widely explored as a strategy to improve mechanical properties of flexible organic electronics. However, phase separation due to the immiscibility of these polymers has limited their effectiveness. In this study, we report the discovery of multiple non‐covalent interactions that enhances the miscibility between insulating and conjugated polymers, resulting in improved mechanical properties. Specifically, we have added polyvinyl chloride (PVC) into the conjugated polymer PM6 and observed a significant increase in solution viscosity, indicative of favorable miscibility between these two polymers. This phenomenon has been rarely observed in other insulating/conjugated polymer composites. Thin films of PM6/PVC exhibit a much‐improved crack‐onset strain of 19.35 %, compared to 10.12 % for pristine PM6 films. Analysis reveal that a "cyclohexyl‐like" structure formed through dipole‐dipole interactions and hydrogen bonding between PVC and PM6 acted as a cross‐linking site in the thin films, leading to improved mechanical properties. Moreover, PM6/PVC blend films have demonstrated excellent thermal and bending stability when applied as an electron donor in organic solar cells. These findings provide new insights into non‐covalent interactions that can be utilized to enhance the properties of conjugated polymers and may have potential applications in flexible organic electronics. [ABSTRACT FROM AUTHOR]

With their bent π‐systems, cyclic conjugation and inherent cavities, conjugated nanohoops are attractive for organic electronics applications. For ease of processing and morphological stability, an incorporation into polymers is desirable, but to date was hampered with few exceptions by synthetic difficulties. We herein present a unique strategy for the synthesis of conjugated nanohoop polymers using a dibenzo[a,e]pentalene (DBP) as central connector. We demonstrate this versatility by synthesizing three electronically diverse copolymers with dithienyldiketo(pyrrolopyrrol), fluorene and carbazole comonomers, and report the first donor‐acceptor nanohoop polymer. Optoelectronic investigations reveal the prevalence of cyclic or linear conjugation, depending on the comonomer unit, and ambipolar electrochemical properties through the antiaromatic character of the DBP units. As the first report on using conjugated nanohoops for charge storage as positive electrode materials, we show a significant improvement in battery performance in a nanohoop‐containing polymer compared to an equivalent nanohoop‐free reference polymer. We believe this study will pave the way for the synthesis of a diverse range of nanohoop polymers and further stimulate their exploration for charge storage in batteries. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Solar‐driven synthesis of hydrogen peroxide (H2O2) from water and air provides a low‐cost and eco‐friendly alternative route to the traditional anthraquinone method. Herein, four thiazole‐based conjugated polymers (Tz‐CPs: TTz, BTz, TBTz and BBTz) are synthesized via aldimine condensation. BBTz exhibits the highest H2O2 production rate of 7274 μmol g−1 h−1 in pure water. Further, the reaction path is analyzed by electron paramagnetic resonance (EPR), in situ diffuse reflectance infrared Fourier transform (DRIFT) and theoretical calculation, highlighting the prominent role of singlet oxygen (1O2). The generation of 1O2 occurs through the oxidation of superoxide radical (⋅O2−) and subsequent conversion into endoperoxides via [4+2] cycloaddition over BBTz, which promotes charge separation and reduces the barrier for H2O2 production. This work provides new insight into the mechanism of photocatalytic O2 reduction and the molecular design of superior single‐polymer photocatalysts. [ABSTRACT FROM AUTHOR]

The Suzuki–Miyaura cross‐coupling is one of the most important and powerful methods for constructing C−C bonds. However, the protodeboronation of arylboronic acids hinder the development of Suzuki–Miyaura coupling in the precise synthesis of conjugated polymers (CPs). Here, an anhydrous room temperature Suzuki–Miyaura cross‐coupling reaction between (hetero)aryl boronic esters and aryl sulfides was explored, of which universality was exemplified by thirty small molecules and twelve CPs. Meanwhile, the mechanistic studies involving with capturing four coordinated borate intermediate revealed the direct transmetalation of boronic esters in the absence of H2O suppressing the protodeboronation. Additionally, the room temperature reaction significantly reduced the homocoupling defects and enhanced the optoelectronic properties of the CPs. In all, this work provides a green protocol to synthesize alternating CPs. [ABSTRACT FROM AUTHOR]

The emergence of two‐dimensional conjugated metal–organic frameworks (2D c‐MOFs) with pronounced electrical properties (e.g. high conductivity) has provided a novel platform for efficient energy storage, sensing, and electrocatalysis. Nevertheless, the limited availability of suitable ligands restricts the number of available types of 2D c‐MOFs, especially those with large pore apertures and high surface areas are rare. Herein, we develop two new 2D c‐MOFs (HIOTP‐M, M=Ni, Cu) employing a large p‐π conjugated ligand of hexaamino‐triphenyleno[2,3‐b:6,7‐b′:10,11‐b′′]tris[1,4]benzodioxin (HAOTP). Among the reported 2D c‐MOFs, HIOTP‐Ni exhibits the largest pore size of 3.3 nm and one of the highest surface areas (up to 1300 m2 g−1). As an exemplary application, HIOTP‐Ni has been used as a chemiresistive sensing material and displays high selective response (405 %) and a rapid response (1.69 min) towards 10 ppm NO2 gas. This work demonstrates significant correlation linking the pore aperture of 2D c‐MOFs to their sensing performance. [ABSTRACT FROM AUTHOR]

A third component featuring a planar backbone structure similar to the binary host molecule has been the preferred ingredient for improving the photovoltaic performance of ternary organic solar cells (OSCs). In this work, we explored a new avenue that introduces 3D‐structured molecules as guest acceptors. Spirobifluorene (SF) is chosen as the core to combine with three different terminal‐modified (rhodanine, thiazolidinedione, and dicyano‐substituted rhodanine) benzotriazole (BTA) units, affording three four‐arm molecules, SF‐BTA1, SF‐BTA2, and SF‐BTA3, respectively. After adding these three materials to the classical system PM6 : Y6, the resulting ternary devices obtained ultra‐high power‐conversion efficiencies (PCEs) of 19.1 %, 18.7 %, and 18.8 %, respectively, compared with the binary OSCs (PCE=17.4 %). SF‐BTA1‐3 can work as energy donors to increase charge generation via energy transfer. In addition, the charge transfer between PM6 and SF‐BTA1‐3 also acts to enhance charge generation. Introducing SF‐BTA1‐3 could form acceptor alloys to modify the molecular energy level and inhibit the self‐aggregation of Y6, thereby reducing energy loss and balancing charge transport. Our success in 3D multi‐arm materials as the third component shows good universality and brings a new perspective. The further functional development of multi‐arm materials could make OSCs more stable and efficient. [ABSTRACT FROM AUTHOR]

Developing high‐performance but low‐cost n‐type polymers remains a significant challenge in the commercialization of organic field‐effect transistors (OFETs). To achieve this objective, it is essential to design the key electron‐deficient units with simple structures and facile preparation processes, which can facilitate the production of low‐cost n‐type polymers. Herein, by sequentially introducing fluorine and cyano functionalities onto trans‐1,3‐butadiene, we developed a series of structurally simple but highly electron‐deficient building blocks, namely 1,4‐dicyano‐butadiene (CNDE), 3‐fluoro‐1,4‐dicyano‐butadiene (CNFDE), and 2,3‐difluoro‐1,4‐dicyano‐butadiene (CNDFDE), featuring a highly coplanar backbone and deep‐positioned lowest unoccupied molecular orbital (LUMO) energy levels (−3.03–4.33 eV), which render them highly attractive for developing n‐type semiconducting polymers. Notably, all these electron‐deficient units can be easily accessed by a two‐step high‐yield synthetic procedure from low‐cost raw materials, thus rendering them highly promising candidates for commercial applications. Upon polymerization with diketopyrrolopyrrole (DPP), three copolymers were developed that demonstrated unipolar n‐type transport characteristics in OFETs with the highest electron mobility of >1 cm2 V−1 s−1. Hence, CNDE, CNFDE, and CNDFDE represent a class of novel, simple, and efficient electron‐deficient units for constructing low‐cost n‐type polymers, thereby providing valuable insight for OFET applications. [ABSTRACT FROM AUTHOR]

Hydrophobic conjugated polymers have poor ionic transport property, so hydrophilic side chains are often grafted for their application as organic electrochemical transistors (OECTs). However, this modification lowers their charge transport ability. Here, an ionic gel interfacial layer is applied to improve the ionic transport while retaining the charge transport ability of the polymers. By using the ionic gels comprising gel matrix and ionic liquids as the interfacial layers, the hydrophobic polymer achieves the OECT feature with high transconductance, low threshold voltage, high current on/off ratio, short switching time, and high operational stability. The working mechanism is also revealed. Moreover, the OECT performance can be tuned by varying the types and ratios of ionic gels. With the proposed ionic gel strategy, OECTs can be effectively realized with hydrophobic conjugated polymers. [ABSTRACT FROM AUTHOR]

Controlling the nanoscale orientation of π‐conjugated systems remains challenging due to the complexity of multiple energy landscapes involved in the supramolecular assembly process. In this study, we have developed an effective strategy for programming the pathways of π‐conjugated supramolecular polymers, by incorporating both electron‐rich methoxy‐ or methanthiol‐benzene as donor unit and electron‐poor cyano‐vinylenes as acceptor units on the monomeric structure. It leads to the formation of parallel‐stacked supramolecular polymers as the metastable species through homomeric donor/acceptor packing, which convert to slip‐stacked supramolecular polymers as the thermodynamically stable species facilitated by heteromeric donor‐acceptor packing. By further investigating the external seed‐induced kinetic‐to‐thermodynamic transformation behaviors, our findings suggest that the donor‐acceptor functionality on the seed structure is crucial for accelerating pathway conversion. This is achieved by eliminating the initial lag phase in the supramolecular polymerization process. Overall, this study provides valuable insights into designing molecular structures that control aggregation pathways of π‐conjugated nanostructures. [ABSTRACT FROM AUTHOR]

Developing new reactive pathway to activate inert C(sp3)−H bonds for valuable oxygenated products remains a challenge. We prepared a series of triazine conjugated organic polymers to photoactivate C−H into aldehyde/ketone via O2→H2O2→⋅OH→Cl⋅→Cl2⋅−. Experiment results showed Cl2⋅− could successively activate C(sp3)−H more effectively than Cl⋅ to generate unstable dichlorinated intermediates, increasing the kinetic rate ratio of dichlorination to monochlorination by a factor of 2,000 and thus breaking traditional dichlorination kinetic constraints. These active intermediates were hydrolyzed into aldehydes or ketones easily, when compared with typical stable dichlorinated complexes, avoiding chlorinated by‐product generation. Moreover, an integrated two‐phase system in an acid solution strengthened the Cl2⋅− mediated process and inhibited product overoxidation, where the conversion rate of toluene reached 16.94 mmol/g/h and the selectivity of benzaldehyde was 99.5 %. This work presents a facile and efficient approach for selective conversion of inert C(sp3)−H bonds using Cl2⋅−. [ABSTRACT FROM AUTHOR]

The development of conjugated polymers especially n‐type polymer semiconductors is powered by the design and synthesis of electron‐deficient building blocks. Herein, a strong acceptor building block with di‐metallaaromatic structure was designed and synthesized by connecting two electron‐deficient metallaaromatic units through a π‐conjugated bridge. Then, a double‐monomer polymerization methodology was developed for inserting it into conjugated polymer scaffolds to yield metallopolymers. The isolated well‐defined model oligomers indicated polymer structures. Kinetic studies based on nuclear magnetic resonance and ultraviolet–visible spectroscopies shed light on the polymerization process. Interestingly, the resulted metallopolymers with dπ–pπ conjugations are very promising electron transport layer materials which can boost photovoltaic performance of an organic solar cell, with power conversion efficiency up to 18.28 % based on the PM6 : EH‐HD‐4F non‐fullerene system. This work not only provides a facile route to construct metallaaromatic conjugated polymers with various functional groups, but also discovers their potential applications for the first time. [ABSTRACT FROM AUTHOR]

π‐Conjugated aromatic polymers (πCAPs) are central components of functional materials yet suffer from insolubility without multiple covalent substituents on their backbones. We herein disclose a new strategy for the facile processing of unsubstituted heterocyclic πCAPs (i.e. poly(para‐phenylene‐2,6‐benzobisoxazole) and poly(benzimidazobenzo‐phenanthroline)), independent of the polymer length, via non‐covalent encircling with aromatic micelles, composed of bent aromatic amphiphiles, in water. The UV/Visible studies reveal that the efficiencies of the present encircling method are ≈10 to 50‐fold higher than those using conventional amphiphiles under the same conditions. The AFM and SEM analyses of the resultant aqueous polymer composites show that otherwise insoluble πCAPs form fine bundles (e.g. ≈1 nm in thickness) in the tubular aromatic micelles, through efficient π‐stacking interactions. In the same way, pristine poly(para‐phenylene) can be dissolved in water, displaying enhanced fluorescence (10‐fold), relative to the polymer solid. Two types of unsubstituted πCAPs are likewise co‐encircled in water, indicated by UV/Visible analysis. Importantly, aqueous processing of the encircled πCAPs into free‐standing single‐ or multicomponent films with submicrometer thickness is demonstrated through a simple filtration‐annealing protocol. [ABSTRACT FROM AUTHOR]

Clusteroluminescence (CL) and through‐space interactions (TSIs) of non‐conjugated molecules have drawn more attention due to their unique photophysical behaviors that are different from largely conjugated luminogens. However, achieving red and even near‐infrared (NIR) emission from such systems is still challenging due to the intrinsic drawbacks of non‐conjugated molecules and the lack of theories for structure–property relationships. In this work, six phenolic resins are designed and synthesized based on two molecule‐engineering strategies: increasing the number of TSIs units and introducing electron‐donating/‐withdrawing groups. All phenolic resins are verified as luminogens with CL property (CLgens), and the first example of CLgens with NIR emission (maximum emission wavelength ≥680 nm) and high absolute quantum yield (47 %) is reported. Experiments and theoretical analysis reveal that two TSIs types, through‐space locally excited state and through‐space charge transfer state, play essential roles in achieving CL from these non‐conjugated polymers, which could be manipulated via changing structural conformation and electron density or altering electron transition behaviors. This work not only provides an approach to manipulate TSIs and CL of non‐conjugated polymers but also endows commercially available phenolic resins with high practical value as luminescence materials. [ABSTRACT FROM AUTHOR]

The S‐glycosyltransferase LmbT, involved in the biosynthesis of lincomycin A, is the only known enzyme that catalyzes the enzymatic incorporation of rare amino acid L‐ergothioneine (EGT) into secondary metabolites. Here, we show the structure and function analyses of LmbT. Our in vitro analysis of LmbT revealed that the enzyme shows promiscuous substrate specificity toward nitrogenous base moieties in the generation of unnatural nucleotide diphosphate (NDP)‐D‐α‐D‐lincosamides. Furthermore, the X‐ray crystal structures of LmbT in its apo form and in complex with substrates indicated that the large conformational changes of the active site occur upon binding of the substrates, and that EGT is strictly recognized by salt‐bridge and cation‐π interactions with Arg260 and Trp101, respectively. The structure of LmbT in complex with its substrates, the docking model with the EGT‐S‐conjugated lincosamide, and the structure‐based site‐directed mutagenesis analysis revealed the structural details of the LmbT‐catalyzed SN2‐like S‐glycosylation reaction with EGT. [ABSTRACT FROM AUTHOR]

Ionic organic crystals containing organic planar π‐conjugated units has become one of the hot spots as nonlinear optical (NLO) materials. However, although this type of ionic organic NLO crystals commonly have remarkable second harmonic generation (SHG) responses, they also suffer from overlarge birefringences and relatively small band gaps that be hardly beyond 6.2 eV. Herein, a flexible π‐conjugated [C3H(CH3)O4]2− unit was theoretically revealed, showing great potential for designing NLO crystals with balanced optical properties. Accordingly, through the reasonable NLO‐favourable layered design, a new ionic organic material, NH4[LiC3H(CH3)O4], was successfully obtained. As expected, it achieves not only a large SHG effect (4×KDP), but also a suitable birefringence (0.06@546 nm) and an ultrawide band gap (>6.5 eV). This study provides a new flexible π‐conjugated NLO‐active unit, contributing to design more ionic organic NLO materials with excellent balanced optical properties. [ABSTRACT FROM AUTHOR]

Hole transport materials (HTMs) are a key component of perovskite solar cells (PSCs). The small molecular 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenyl)‐amine‐9,9′‐spirobifluorene (spiro‐OMeTAD, termed "Spiro") is the most successful HTM used in PSCs, but its versatility is imperfect. To improve its performance, we developed a novel spiro‐type HTM (termed "DP") by substituting four anisole units on Spiro with 4‐methoxybiphenyl moieties. By extending the π‐conjugation of Spiro in this way, the HOMO level of the HTM matches well with the perovskite valence band, enhancing hole mobility and increasing the glass transition temperature. DP‐based PSC achieves high power conversion efficiencies (PCEs) of 25.24 % for small‐area (0.06 cm2) devices and 21.86 % for modules (designated area of 27.56 cm2), along with the certified efficiency of 21.78 % on a designated area of 27.86 cm2. The encapsulated DP‐based devices maintain 95.1 % of the initial performance under ISOS‐L‐1 conditions after 2560 hours and 87 % at the ISOS‐L‐3 conditions over 600 hours. [ABSTRACT FROM AUTHOR]

Since the breakthrough of conductive polymers in 1977, scientists have made great efforts to create small band gap (Eg) conjugated polymers. Two general strategies to design small Eg conjugated polymers are quinoid structure and donor‐acceptor structure. Ultrasmall Eg conjugated polymers (Eg<1.0 eV) always suffer from poor air stability because of high‐lying HOMO energy levels. In this work, we report a new strategy to design ultrasmall Eg conjugated polymers by N−B←N unit, i.e. balanced resonant boron‐nitrogen covalent bond (B−N) and boron‐nitrogen coordination bond (B←N). The resulting polymer exhibits an Eg of 0.82 eV and an onset absorption wavelength of >1500 nm. Moreover, the polymer exhibits excellent air stability because of its low‐lying LUMO/HOMO energy levels. An unprecedented property of this polymer is the selective light absorption in the infrared range (800–1500 nm) and high transparency in the visible range (400–780 nm). Using this property, for the first time, we demonstrate the application of conjugated polymers as transparent thermal‐shielding coating layer on glass, which reduces indoor solar irradiation through window and consequently reduces power consumption for cooling of buildings and cars in summer. [ABSTRACT FROM AUTHOR]

Despite significant progress in the preparation and characterization of two‐dimensional (2D) materials, the synthesis of 2D organic materials remains challenging. Here, we report a novel space‐confined polymerization method that enables the large‐scale synthesis of 2D sheets of a functional conjugated polymer, namely, poly(3,4‐ethylenedioxythiophene) (PEDOT). A key step in this method is the confinement of monomer to the boundaries of ice crystals using micelles. This spatial confinement directs the polymerization to form 2D PEDOT sheets with high crystallinity and controlled morphology. Supercapacitors prepared from the 2D PEDOT sheets exhibit outstanding performance metrics. In aqueous electrolyte, a high areal specific capacitance of 898 mF cm−2 at 0.2 mA cm−2 along with an excellent rate capability is achieved (e.g. capacitance retention of 67.6 % at a 50‐fold higher current). Moreover, the 2D PEDOT‐based supercapacitors exhibit outstanding cycling stability (capacitance retention of 98.5 % after 30,000 cycles). Device performance is further improved when an organic electrolyte is used. [ABSTRACT FROM AUTHOR]

The development of conjugated polymers with high semiconducting performance and high reliability is of great significance for flexible electronics. Herein, we developed a new type of electron‐accepting building block; i.e. non‐symmetric half‐fused B←N coordinated diketopyrrolopyrrole (DPP) (HBNDPP), for amorphous conjugated polymers toward flexible electronics. The rigid B←N fusion part of HBNDPP endows the resulting polymers with decent electron transport, while its non‐symmetric structure causes the polymer to exhibit multiple conformation isomers with flat torsional potential energies. Thus, it gets packed in an amorphous manner in solid state, ensuring good resistance to bending strain. Combined with hardness and softness, the flexible organic field‐effect transistor devices exhibit n‐type charge properties with decent mobility, good bending resistance, and good ambient stability. The preliminary study makes this building block a potential candidate for future design of conjugated materials for flexible electronic devices. [ABSTRACT FROM AUTHOR]