Polyolefins are among the most important large-scale polymers. High-temperature solution polymerization is one of the most effective methods for preparing high-performance polyolefins. Although advanced high-temperature solution copolymerization of ethylene and polar olefins (especially acrylates) is highly desirable for producing value-added polar polyolefins, it poses significant challenges in chemistry and catalysis, including low catalyst thermostability and low polymer molecular weight at temperatures exceeding 100°C. To address these issues, this study proposes design principles for an innovative neutral α-ketocarboxamide nickel catalyst platform rather than modifying previously reported nickel catalysts. This new generation of nickel catalysts not only offers inherent advantages, including facile synthesis, air stability, and exceptional thermostability (150°C), but also enables high-temperature solution copolymerization of ethylene and acrylates (methyl, n-butyl, and tert-butyl acrylates), producing high-molecular-weight copolymers without the need for cocatalysts. At the industrially preferred 110°C–150°C, ethylene–acrylate copolymers with molecular weights of 103–627 kDa were obtained, which are 4–19 times higher than those produced by previous catalysts. Transitioning from low- to high-molecular-weight ethylene–acrylate copolymers is vital for practical industrial applications. Mechanistic insights revealed the feasibility of ethylene–acrylate copolymerization. Overall, this study establishes a conceptual foundation for high-temperature solution copolymerization of ethylene and acrylates.
{"title":"A Facile Neutral Nickel Catalyst Platform for High-Temperature Solution Copolymerization of Ethylene and Acrylate","authors":"Xiaoqiang Hu, Jingmin Chen, Qiankun Li, Xiaohui Kang, Zhongbao Jian","doi":"10.1002/anie.202525742","DOIUrl":"https://doi.org/10.1002/anie.202525742","url":null,"abstract":"Polyolefins are among the most important large-scale polymers. High-temperature solution polymerization is one of the most effective methods for preparing high-performance polyolefins. Although advanced high-temperature solution copolymerization of ethylene and polar olefins (especially acrylates) is highly desirable for producing value-added polar polyolefins, it poses significant challenges in chemistry and catalysis, including low catalyst thermostability and low polymer molecular weight at temperatures exceeding 100°C. To address these issues, this study proposes design principles for an innovative neutral α-ketocarboxamide nickel catalyst platform rather than modifying previously reported nickel catalysts. This new generation of nickel catalysts not only offers inherent advantages, including facile synthesis, air stability, and exceptional thermostability (150°C), but also enables high-temperature solution copolymerization of ethylene and acrylates (methyl, <i>n</i>-butyl, and <i>tert</i>-butyl acrylates), producing high-molecular-weight copolymers without the need for cocatalysts. At the industrially preferred 110°C–150°C, ethylene–acrylate copolymers with molecular weights of 103–627 kDa were obtained, which are 4–19 times higher than those produced by previous catalysts. Transitioning from low- to high-molecular-weight ethylene–acrylate copolymers is vital for practical industrial applications. Mechanistic insights revealed the feasibility of ethylene–acrylate copolymerization. Overall, this study establishes a conceptual foundation for high-temperature solution copolymerization of ethylene and acrylates.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"31 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The inherent preference of classical type II photosensitizers for generating singlet oxygen (1O2) via energy transfer presents a key challenge in developing type I systems capable of producing superoxide radicals (O2•–) through electron transfer. Herein, we report a porphyrin-based supramolecular organic framework (SOF, TPP-BPY-CB[8]) assembled via host–guest interactions with cucurbit[8]uril (CB[8]), which achieves a significantly enhanced 1O2 quantum yield (94.04%) compared to the monomeric unit TPP-BPY (74.52%). To overcome the energy transfer-dominated reactive oxygen species (ROS) pathway, a series of electron transfer mediators were introduced to modulate the excited-state dynamics, resulting in BQ@TPP-BPY-CB[8] that effectively switches the ROS pathway from type II to type I. This mediator-driven modulation not only enables O2•– production under hypoxic conditions but also expands the functional diversity of the SOF system. The two ROS pathways are selectively leveraged in photocatalytic applications: TPP-BPY-CB[8] excels in 1O2-mediated oxidation of organophosphorus compounds, while BQ@TPP-BPY-CB[8] facilitates highly efficient thiol-ene cross-coupling via O2•– promotion. This work presents a robust strategy for tailoring ROS generation in supramolecular photocatalysis, offering a new design paradigm for multifunctional, ROS-directed photoreactive materials.
{"title":"Electron Transfer Mediator–Enabled Modular Control of 1O2 and O2•– Generation in Porphyrin Supramolecular Frameworks for Selective Photosynthesis","authors":"Wen-Qiang Liu, Fa-Dong Wang, Hui Liu, Ling-Bao Xing","doi":"10.1002/anie.202519699","DOIUrl":"https://doi.org/10.1002/anie.202519699","url":null,"abstract":"The inherent preference of classical type II photosensitizers for generating singlet oxygen (<sup>1</sup>O<sub>2</sub>) via energy transfer presents a key challenge in developing type I systems capable of producing superoxide radicals (O<sub>2</sub><sup>•–</sup>) through electron transfer. Herein, we report a porphyrin-based supramolecular organic framework (SOF, TPP-BPY-CB[8]) assembled via host–guest interactions with cucurbit[8]uril (CB[8]), which achieves a significantly enhanced <sup>1</sup>O<sub>2</sub> quantum yield (94.04%) compared to the monomeric unit TPP-BPY (74.52%). To overcome the energy transfer-dominated reactive oxygen species (ROS) pathway, a series of electron transfer mediators were introduced to modulate the excited-state dynamics, resulting in BQ@TPP-BPY-CB[8] that effectively switches the ROS pathway from type II to type I. This mediator-driven modulation not only enables O<sub>2</sub><sup>•–</sup> production under hypoxic conditions but also expands the functional diversity of the SOF system. The two ROS pathways are selectively leveraged in photocatalytic applications: TPP-BPY-CB[8] excels in <sup>1</sup>O<sub>2</sub>-mediated oxidation of organophosphorus compounds, while BQ@TPP-BPY-CB[8] facilitates highly efficient thiol-ene cross-coupling via O<sub>2</sub><sup>•–</sup> promotion. This work presents a robust strategy for tailoring ROS generation in supramolecular photocatalysis, offering a new design paradigm for multifunctional, ROS-directed photoreactive materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"44 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
According to Neumann's Principle, the chiral-polar photovoltaic effect (CPPE) is restricted to crystals in one of the five chiral ferroelectric space groups—based on the assumption of perfect long-range periodicity and bulk symmetry. However, this framework overlooks symmetry breaking at crystal boundaries. Herein, we report the emergence of surface ferroelectricity in a one-dimensional chiral nonferroelectric perovskite, R/S-MPZSbBr5 (MPZ = 2-methylpiperazine), achieved through interlayer antiparallel alignment of polar Sb–Br chains. The bulk structure adopts a nonferroelectric phase with alternating polar domains, resulting in net-zero polarization. Yet, at the (001) surface, the breaking of continuous translational symmetry gives rise to local ferroelectricity. This surface-driven polarization, coupled with the intrinsic chirality of the crystal, enables a localized CPPE. Moreover, the synergy between surface ferroelectricity and pyro-photovoltaic effects significantly enhances the performance of self-powered circularly polarized light (CPL) detection. Our work reveals the limitations of Neumann's Principle at crystal interfaces and opens new avenues for engineering ferroelectricity and chiral optoelectronics in nonferroelectric systems.
{"title":"Surface Ferroelectricity in Lead-Free Nonferroelectric Chiral Perovskites Beyond Neumann's Principle","authors":"Zhi Yang, Yunlong Bai, Jiandong Yao, Yangding Qiu, Qihang Deng, Jie Wu, Guankui Long, Bingsuo Zou, Jia Hong Pan, Ruosheng Zeng","doi":"10.1002/anie.9911471","DOIUrl":"https://doi.org/10.1002/anie.9911471","url":null,"abstract":"According to Neumann's Principle, the chiral-polar photovoltaic effect (CPPE) is restricted to crystals in one of the five chiral ferroelectric space groups—based on the assumption of perfect long-range periodicity and bulk symmetry. However, this framework overlooks symmetry breaking at crystal boundaries. Herein, we report the emergence of surface ferroelectricity in a one-dimensional chiral nonferroelectric perovskite, <i>R</i>/<i>S</i>-MPZSbBr<sub>5</sub> (MPZ = 2-methylpiperazine), achieved through interlayer antiparallel alignment of polar Sb–Br chains. The bulk structure adopts a nonferroelectric phase with alternating polar domains, resulting in net-zero polarization. Yet, at the (001) surface, the breaking of continuous translational symmetry gives rise to local ferroelectricity. This surface-driven polarization, coupled with the intrinsic chirality of the crystal, enables a localized CPPE. Moreover, the synergy between surface ferroelectricity and pyro-photovoltaic effects significantly enhances the performance of self-powered circularly polarized light (CPL) detection. Our work reveals the limitations of Neumann's Principle at crystal interfaces and opens new avenues for engineering ferroelectricity and chiral optoelectronics in nonferroelectric systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"397 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chayanan Tangsombun,Amy Simpson,Rebecca L Charlton,Lucy E Sabin,Paul G Genever,David K Smith
We report the synthesis and characterization of a simple alcohol-functionalized low-molecular-weight gelator (LMWG) based on a 1,3:2,4-dibenzylidenesorbitol scaffold (DBS-CH2OH) and explore its self-assembly in comparison to acylhydrazide-functionalized DBS-CONHNH2. DBS-CH2OH forms a stiffer, highly organized, less-soluble self-assembled hydrogel, with a different assembly mode and much higher entropy/enthalpy of dissociation. On mixing, the LMWGs co-assemble into gel nanofibers with similar thermodynamics to DBS-CONHNH2. DBS-CH2OH is an excellent scaffold for the growth of human mesenchymal stem cells (hMSCs), which exhibit extended spread-shaped morphologies on the gel surface. In contrast, for DBS-CONHNH2, hMSCs have a rounded morphology and penetrate into the softer gel. A simple functional group change on the LMWG, therefore, leads to a remarkable change in cell growth outcomes. When hMSCs are grown on the co-assembled gel, they have the rounded morphology characteristic of DBS-CONHNH2 but remain on the gel surface, like DBS-CH2OH. The multi-component gel thus shares characteristics of the individual LMWGs, with hMSC growth being controlled by factors like structure, stiffness, and dynamics. This work demonstrates how chemical manipulation of gels based on deceptively simple LMWGs can have profound impacts in biomaterials engineering.
{"title":"Molecular-Scale Tuning of Low-Molecular-Weight Gelators Controls Supramolecular Assembly and Directs Human Mesenchymal Stem Cell Growth.","authors":"Chayanan Tangsombun,Amy Simpson,Rebecca L Charlton,Lucy E Sabin,Paul G Genever,David K Smith","doi":"10.1002/anie.202523454","DOIUrl":"https://doi.org/10.1002/anie.202523454","url":null,"abstract":"We report the synthesis and characterization of a simple alcohol-functionalized low-molecular-weight gelator (LMWG) based on a 1,3:2,4-dibenzylidenesorbitol scaffold (DBS-CH2OH) and explore its self-assembly in comparison to acylhydrazide-functionalized DBS-CONHNH2. DBS-CH2OH forms a stiffer, highly organized, less-soluble self-assembled hydrogel, with a different assembly mode and much higher entropy/enthalpy of dissociation. On mixing, the LMWGs co-assemble into gel nanofibers with similar thermodynamics to DBS-CONHNH2. DBS-CH2OH is an excellent scaffold for the growth of human mesenchymal stem cells (hMSCs), which exhibit extended spread-shaped morphologies on the gel surface. In contrast, for DBS-CONHNH2, hMSCs have a rounded morphology and penetrate into the softer gel. A simple functional group change on the LMWG, therefore, leads to a remarkable change in cell growth outcomes. When hMSCs are grown on the co-assembled gel, they have the rounded morphology characteristic of DBS-CONHNH2 but remain on the gel surface, like DBS-CH2OH. The multi-component gel thus shares characteristics of the individual LMWGs, with hMSC growth being controlled by factors like structure, stiffness, and dynamics. This work demonstrates how chemical manipulation of gels based on deceptively simple LMWGs can have profound impacts in biomaterials engineering.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"54 1","pages":"e23454"},"PeriodicalIF":16.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146042521","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kayleigh S van Esterik,Tommaso Marchetti,Sijbren Otto
Catalysis of bond-forming reactions is key to the development of life-like chemical systems as it allows to build up new material, increasing molecular complexity and diversity. Integrating catalysis with other characteristic properties of life, like self-replication, represents an important advance in the transition from chemistry to life. We have previously shown that catalysis can emerge in synthetic self-replicators that form through supramolecular assembly. However, the organocatalyzed reactions were solely bond-breaking so far. We now report the successful expansion of the catalytic promiscuity of these systems to bond-forming reactions. We show that a self-replicator efficiently catalyzes acyl hydrazone formation between different hydrazides and aldehydes. This marks an important step towards the further development of evolvable systems that combine metabolic activity with self-replication.
{"title":"Building Molecules by a Self-Replicator That Catalyzes Acyl Hydrazone Formation.","authors":"Kayleigh S van Esterik,Tommaso Marchetti,Sijbren Otto","doi":"10.1002/anie.202506986","DOIUrl":"https://doi.org/10.1002/anie.202506986","url":null,"abstract":"Catalysis of bond-forming reactions is key to the development of life-like chemical systems as it allows to build up new material, increasing molecular complexity and diversity. Integrating catalysis with other characteristic properties of life, like self-replication, represents an important advance in the transition from chemistry to life. We have previously shown that catalysis can emerge in synthetic self-replicators that form through supramolecular assembly. However, the organocatalyzed reactions were solely bond-breaking so far. We now report the successful expansion of the catalytic promiscuity of these systems to bond-forming reactions. We show that a self-replicator efficiently catalyzes acyl hydrazone formation between different hydrazides and aldehydes. This marks an important step towards the further development of evolvable systems that combine metabolic activity with self-replication.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":"e06986"},"PeriodicalIF":16.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146042520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hydrogen-atom transfer (HAT) lies at the heart of radical chemistry, yet asymmetric HAT has been difficult because the high reactivity of radicals often forces H-transfer to proceed through early, weakly organized transition states, yielding small ΔΔG‡ and allowing rapid racemic background pathways to compete. Recent advances across small-molecule, metalloradical, cooperative, peptide, and enzymatic catalysis show that high enantioselectivity is attainable when the catalyst is engineered to exert stereocontrol precisely at the H-transfer step that sets configuration. In this minireview, we organize asymmetric HAT into five regimes-donation-controlled termination, radical-centered control, abstraction-controlled HAT, cooperative bimetallic catalysis, and enzyme-mediated HAT-each specified by where chiral information is introduced during H-transfer. Through representative cases, we illustrate how catalysts achieve enantioselection by defining radical geometry, guiding H-delivery, enforcing selective hydrogen abstraction, or confining donor-acceptor pairs within organized chiral environments. This mechanistic framework provides a unified lens spanning synthetic and biocatalytic systems, clarifies the distinct stereochemical logics in each regime, and highlights emerging opportunities for expanding asymmetric radical chemistry through precisely orchestrated H-atom transfer.
{"title":"Where Enantioselection is Set: A Mechanistic Framework for Asymmetric Hydrogen-Atom Transfer.","authors":"Zhongyun Xu,Yufeng Yang,Yong-Qiang Zhang","doi":"10.1002/anie.202526135","DOIUrl":"https://doi.org/10.1002/anie.202526135","url":null,"abstract":"Hydrogen-atom transfer (HAT) lies at the heart of radical chemistry, yet asymmetric HAT has been difficult because the high reactivity of radicals often forces H-transfer to proceed through early, weakly organized transition states, yielding small ΔΔG‡ and allowing rapid racemic background pathways to compete. Recent advances across small-molecule, metalloradical, cooperative, peptide, and enzymatic catalysis show that high enantioselectivity is attainable when the catalyst is engineered to exert stereocontrol precisely at the H-transfer step that sets configuration. In this minireview, we organize asymmetric HAT into five regimes-donation-controlled termination, radical-centered control, abstraction-controlled HAT, cooperative bimetallic catalysis, and enzyme-mediated HAT-each specified by where chiral information is introduced during H-transfer. Through representative cases, we illustrate how catalysts achieve enantioselection by defining radical geometry, guiding H-delivery, enforcing selective hydrogen abstraction, or confining donor-acceptor pairs within organized chiral environments. This mechanistic framework provides a unified lens spanning synthetic and biocatalytic systems, clarifies the distinct stereochemical logics in each regime, and highlights emerging opportunities for expanding asymmetric radical chemistry through precisely orchestrated H-atom transfer.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"71 1","pages":"e26135"},"PeriodicalIF":16.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146042517","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Doping heteroatoms with non-typical electronic couplings offered the great opportunity to fine-tune chemical structures and optoelectronic properties of organic π-conjugated molecules (OCMs). Herein, we reported the first example of hybrid COPN multiple-resonance (MR) thermally activated delayed fluorescence (TADF) emitters via the modular protocols. Compared with the classical BN/CON MR-emitters having p-π conjugation, new COPN MR-emitters maintained the various n/σ/σ*-π* hyperconjugation via the P-center. Collaboratively with CO group, the P-regulated (lp, O, S, and Me+) hyperconjugation maintained the strong impacts on the TADF properties, such as FWHM, ISC/RISC, and PLQY. The dominating short-range (SR) N➞CO charge-transfer (CT) character suggested the CON-type MR structure in the PO-derivative. The strong long-range (LR) P➞CO CT character suggested the COP-type MR structure in the P(III)-derivative. Leveraging on the self-amplified PO-hyperconjugation, the double-PO derivative exhibited the dominating PON-type MR-TADF involving the SR N➞PO CT. The increased PLQYs (54%) and narrowed emission (FWHM: 13 nm) are among the best CON-type MR-emitters in the literature. As a proof of concept, the 1st generation hybrid MR-emitters were applied as the light-emitting materials in organic lighting-emitting diodes that showed the narrow-band blue (FWHM: 26 nm) and cyan emission (FWHM: 17 nm) with EQE as high as 7.3% and 22.8%, respectively. The current study revealed that installing the new hybrid conjugation, namely p/n/σ-π coupling into OCMs holds a great promise for designing new types of MR-emitters with excellent TADF characters.
掺杂具有非典型电子耦合的杂原子为精细调整有机π共轭分子（ocm）的化学结构和光电子性质提供了很好的机会。在此，我们通过模块化协议报道了混合COPN多共振（MR）热激活延迟荧光（TADF）发射器的第一个例子。与具有p-π共轭的经典BN/CON磁致发光体相比，新型COPN磁致发光体通过p中心保持了n/σ/σ*-π*的超共轭性。p调控的（lp、O、S和Me+）超偶联与CO基团协同作用，维持了对TADF特性（如FWHM、ISC/RISC和PLQY）的强烈影响。主要的短程（SR） N / CO电荷转移（CT）特征表明po衍生物为con型MR结构。P（III）衍生物的强远程（LR） P- CO CT特征表明其为cop型MR结构。利用自放大的PO-超共轭，双PO衍生物表现出主要的pon型MR-TADF，涉及SR N / PO CT。增加的PLQYs（54%）和缩小的发射（FWHM: 13 nm）是文献中最好的con型mr发射器之一。作为概念验证，第一代混合mr发射器作为发光材料应用于有机发光二极管中，显示出窄带蓝色（FWHM: 26 nm）和青色（FWHM: 17 nm）发射，EQE分别高达7.3%和22.8%。目前的研究表明，将p/n/σ-π耦合安装到ocm中，对于设计具有优异TADF特性的新型mr发射器具有很大的希望。
{"title":"Carbonyl Functionalized Azaphosphinine-Based Multiple-Resonance Emitters via Regulated p/n/σ-π Hybrid Conjugation.","authors":"Chao Li,Lingqiang Meng,Huanchao Gu,Yanrong Jiang,Zhaoxin Liu,Ji Zhang,Yongbo Fu,Hong Meng,Yi Ren","doi":"10.1002/anie.202525404","DOIUrl":"https://doi.org/10.1002/anie.202525404","url":null,"abstract":"Doping heteroatoms with non-typical electronic couplings offered the great opportunity to fine-tune chemical structures and optoelectronic properties of organic π-conjugated molecules (OCMs). Herein, we reported the first example of hybrid COPN multiple-resonance (MR) thermally activated delayed fluorescence (TADF) emitters via the modular protocols. Compared with the classical BN/CON MR-emitters having p-π conjugation, new COPN MR-emitters maintained the various n/σ/σ*-π* hyperconjugation via the P-center. Collaboratively with CO group, the P-regulated (lp, O, S, and Me+) hyperconjugation maintained the strong impacts on the TADF properties, such as FWHM, ISC/RISC, and PLQY. The dominating short-range (SR) N➞CO charge-transfer (CT) character suggested the CON-type MR structure in the PO-derivative. The strong long-range (LR) P➞CO CT character suggested the COP-type MR structure in the P(III)-derivative. Leveraging on the self-amplified PO-hyperconjugation, the double-PO derivative exhibited the dominating PON-type MR-TADF involving the SR N➞PO CT. The increased PLQYs (54%) and narrowed emission (FWHM: 13 nm) are among the best CON-type MR-emitters in the literature. As a proof of concept, the 1st generation hybrid MR-emitters were applied as the light-emitting materials in organic lighting-emitting diodes that showed the narrow-band blue (FWHM: 26 nm) and cyan emission (FWHM: 17 nm) with EQE as high as 7.3% and 22.8%, respectively. The current study revealed that installing the new hybrid conjugation, namely p/n/σ-π coupling into OCMs holds a great promise for designing new types of MR-emitters with excellent TADF characters.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"31 1","pages":"e25404"},"PeriodicalIF":16.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146042518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Coordination of a Lewis base to a tricoordinate boryl group generates a tetracoordinate species, thereby inverting the electronic character of the boryl substituents from electron-accepting to electron-donating. Utilizing this π-umpolung strategy, we report temperature-responsive fluorophores that emit in the near-infrared (NIR) region. To achieve reversible π-umpolung, we designed a diarylboryl unit in which two aryl rings are tethered by an alkenyl linker. This alkenyl-strapped scaffold engages in a weak olefin-borane interaction and undergoes frustrated Lewis pair (FLP)-type addition even with bulky neutral Lewis bases such as tricyclohexylphosphine (PCy3). When boryl groups are installed at both termini of 4,7-di(2-thienyl)-2,1,3-benzothiadiazole, coordination of PCy3 induces pronounced red-shifts in the emission spectra. In polar acetonitrile, the emission maximum reaches 732 nm, entering the NIR region. This red shift arises from the strong σ-donating character of the resulting tetracoordinate boron centers, which enhance intramolecular charge transfer (ICT) character in the excited state. Unlike conventional dimesitylborane-fluoride complexes, the FLP-type adducts exhibit reversible, temperature-dependent shifts in the dissociation/association equilibrium. Although the solvent polarity influences the equilibrium, modulation of phosphine Lewis basicity enables reversible dissociation even in polar media, allowing this system to display large emission changes spanning the visible to NIR region.
{"title":"Temperature-Responsive Near-Infrared Emission Enabled by Reversible π-Umpolung with an Alkenyl-Strapped Diarylboryl Unit.","authors":"Satoru Kitamura,Mika Sakai,Shigehiro Yamaguchi","doi":"10.1002/anie.202523338","DOIUrl":"https://doi.org/10.1002/anie.202523338","url":null,"abstract":"Coordination of a Lewis base to a tricoordinate boryl group generates a tetracoordinate species, thereby inverting the electronic character of the boryl substituents from electron-accepting to electron-donating. Utilizing this π-umpolung strategy, we report temperature-responsive fluorophores that emit in the near-infrared (NIR) region. To achieve reversible π-umpolung, we designed a diarylboryl unit in which two aryl rings are tethered by an alkenyl linker. This alkenyl-strapped scaffold engages in a weak olefin-borane interaction and undergoes frustrated Lewis pair (FLP)-type addition even with bulky neutral Lewis bases such as tricyclohexylphosphine (PCy3). When boryl groups are installed at both termini of 4,7-di(2-thienyl)-2,1,3-benzothiadiazole, coordination of PCy3 induces pronounced red-shifts in the emission spectra. In polar acetonitrile, the emission maximum reaches 732 nm, entering the NIR region. This red shift arises from the strong σ-donating character of the resulting tetracoordinate boron centers, which enhance intramolecular charge transfer (ICT) character in the excited state. Unlike conventional dimesitylborane-fluoride complexes, the FLP-type adducts exhibit reversible, temperature-dependent shifts in the dissociation/association equilibrium. Although the solvent polarity influences the equilibrium, modulation of phosphine Lewis basicity enables reversible dissociation even in polar media, allowing this system to display large emission changes spanning the visible to NIR region.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"214 1","pages":"e23338"},"PeriodicalIF":16.6,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146042519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The alkaline hydrogen evolution reaction (HER) associated with anion exchange membrane water electrolyzers (AEMWEs) is kinetically hindered by sluggish water dissociation and complex intermediate adsorption, which previous reports have inadequately addressed through isolated optimization, neglecting the intrinsic coupling between HER elementary steps. Herein, we report a frustrated Lewis pairs (FLPs) catalyst comprising NiRu dual single-atoms and adjacent NiRu nanoclusters anchored on nitrogen-doped carbon (Ni1Ru1-NiRu@NC), mimicking the enzymatic positive feedback mechanism that drives a self-reinforcing catalytic cycle and accelerates the coupled elementary steps in a cascade manner. The catalyst featuring spatially proximate Lewis acid and base sites enable sequential reaction steps, where water dissociation occurs at acid sites and hydrogen adsorption proceed at base sites. The two steps are bridged through rapid hydrogen spillover channel, constructing a closed catalytic circuit in which hydrogen consumption at base sites promotes continuous water dissociation at acid sites. Benefiting from this positive feedback loop, Ni1Ru1-NiRu@NC achieves a remarkable HER performance and exhibits exceptional long-term durability (>1000 h at 1.0 A cm- 2) in AEMWEs. Our findings demonstrate a new strategy to integrate positive feedback-driven, cascade-coupled catalysis in FLPs systems, offering a promising pathway toward high-performance alkaline HER catalysts for industrial application.
与阴离子交换膜水电解槽（AEMWEs）相关的碱性析氢反应（HER）受到缓慢的水解离和复杂的中间吸附的动力学阻碍，以往的报道没有通过孤立优化来充分解决这一问题，忽略了HER基本步骤之间的内在耦合。在此，我们报道了一种挫折路易斯对（FLPs）催化剂，包括NiRu双单原子和相邻的NiRu纳米团簇锚定在氮掺杂的碳上（Ni1Ru1-NiRu@NC），模拟酶的正反馈机制，驱动自我强化的催化循环，并以级联方式加速耦合的基本步骤。催化剂具有空间上近似的刘易斯酸和碱位点，使得反应步骤顺序，其中酸位点发生水解离，碱位点进行氢吸附。这两个步骤通过快速氢溢出通道桥接，构建了一个封闭的催化回路，在这个催化回路中，碱基的氢消耗促进了酸位点的连续水解离。得益于这种正反馈回路，Ni1Ru1-NiRu@NC在AEMWEs中实现了卓越的HER性能，并表现出卓越的长期耐用性（1.0 a cm- 2下bbb1000小时）。我们的研究结果展示了在FLPs系统中集成正反馈驱动的级联催化的新策略，为工业应用的高性能碱性HER催化剂提供了一条有希望的途径。
{"title":"Positive Feedback-Driven NiRu Frustrated Lewis Pairs Catalyst Enables a Self-Reinforcing Catalytic Cycle for Cascade-Coupled Hydrogen Production.","authors":"Kecheng Tong,Liangliang Xu,Xingkun Wang,Cheng Li,Fei Lin,Hanxu Yao,Lei Chu,Peixin Cui,Meng Danny Gu,Heqing Jiang,Minghua Huang","doi":"10.1002/anie.202523215","DOIUrl":"https://doi.org/10.1002/anie.202523215","url":null,"abstract":"The alkaline hydrogen evolution reaction (HER) associated with anion exchange membrane water electrolyzers (AEMWEs) is kinetically hindered by sluggish water dissociation and complex intermediate adsorption, which previous reports have inadequately addressed through isolated optimization, neglecting the intrinsic coupling between HER elementary steps. Herein, we report a frustrated Lewis pairs (FLPs) catalyst comprising NiRu dual single-atoms and adjacent NiRu nanoclusters anchored on nitrogen-doped carbon (Ni1Ru1-NiRu@NC), mimicking the enzymatic positive feedback mechanism that drives a self-reinforcing catalytic cycle and accelerates the coupled elementary steps in a cascade manner. The catalyst featuring spatially proximate Lewis acid and base sites enable sequential reaction steps, where water dissociation occurs at acid sites and hydrogen adsorption proceed at base sites. The two steps are bridged through rapid hydrogen spillover channel, constructing a closed catalytic circuit in which hydrogen consumption at base sites promotes continuous water dissociation at acid sites. Benefiting from this positive feedback loop, Ni1Ru1-NiRu@NC achieves a remarkable HER performance and exhibits exceptional long-term durability (>1000 h at 1.0 A cm- 2) in AEMWEs. Our findings demonstrate a new strategy to integrate positive feedback-driven, cascade-coupled catalysis in FLPs systems, offering a promising pathway toward high-performance alkaline HER catalysts for industrial application.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"102 1","pages":"e23215"},"PeriodicalIF":16.6,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021407","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Despite significant advances in catalytic asymmetric reductive Heck reaction, most reported methods rely on highly reactive aryl electrophiles and exhibit a limited olefin scope. Expanding this transformation to employ more abundant and cost-effective aryl bromides and chlorides with common olefins has remained a major challenge, owing to the inertness of C─Br and C─Cl bonds and the resulting difficulty in achieving chemo-, regio-, and stereocontrol. Here, we report that nickel catalysts combined with chiral dihydroimidazolium-derived N-heterocyclic carbene ligands bearing remote meta-substitution enable highly efficient and enantioselective reductive Heck reaction of a broad range of olefins-including styrenes, 1,3-dienes, and aliphatic alkenes-with aryl bromides and chlorides. Experimental studies and DFT calculations elucidated the origins of stereo induction and structure-reactivity relationships. This robust methodology provides streamlined access to structurally diverse, enantioenriched benzylic frameworks.
{"title":"Nickel-Catalyzed Enantioselective Reductive Heck Reaction of Olefins with Aryl Bromides and Chlorides Enabled by Chiral NHC Ligands.","authors":"Mei-Yu Liu,Kai-Xiang Zhang,Jia-Bin Pan,Qi-Lin Zhou,Li-Jun Xiao","doi":"10.1002/anie.202525600","DOIUrl":"https://doi.org/10.1002/anie.202525600","url":null,"abstract":"Despite significant advances in catalytic asymmetric reductive Heck reaction, most reported methods rely on highly reactive aryl electrophiles and exhibit a limited olefin scope. Expanding this transformation to employ more abundant and cost-effective aryl bromides and chlorides with common olefins has remained a major challenge, owing to the inertness of C─Br and C─Cl bonds and the resulting difficulty in achieving chemo-, regio-, and stereocontrol. Here, we report that nickel catalysts combined with chiral dihydroimidazolium-derived N-heterocyclic carbene ligands bearing remote meta-substitution enable highly efficient and enantioselective reductive Heck reaction of a broad range of olefins-including styrenes, 1,3-dienes, and aliphatic alkenes-with aryl bromides and chlorides. Experimental studies and DFT calculations elucidated the origins of stereo induction and structure-reactivity relationships. This robust methodology provides streamlined access to structurally diverse, enantioenriched benzylic frameworks.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"24 3 1","pages":"e25600"},"PeriodicalIF":16.6,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021406","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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