Jia‐Yin Wang, Ying‐Ying Lei, Jia‐Wang Yuan, Kai Li, Shuang‐Quan Zang
Due to their atomically precise structures and tunable electronic properties, coinage metal clusters have emerged as a significant class of luminescent materials, demonstrating broad application potential in the development of optical sensors and light‐emitting diodes. Recently, luminescent coinage metal clusters exhibiting novel photophysical properties, such as afterglow emission, circularly polarized luminescence, near‐infrared luminescence, and x‐ray excited luminescence, have been successively reported, attracting significant research attention. In this work, the first photo‐responsive luminescent silver cluster ( Ag 8 ) was reported, whose phosphorescence can be activated through UV light irradiation in crystal state. Mechanism study revealed that the photo‐response of Ag 8 was attributed to the photo‐induced oxygen scavenging by methanol within the lattice, which relieved the quenching of the phosphorescence of the metal cluster, leading to a “turn‐on” response. Due to its reversible photoactive luminescent properties in the solid state and excellent stability, a specialized photo‐responsive ink for three‐dimensional printing was developed based on Ag 8 . This study expands the range of luminescent coinage metal clusters and offers a novel strategy for the development of coinage metal cluster‐based stimuli‐responsive materials.
{"title":"Photoactive Luminescence in a Silver Cluster Crystal","authors":"Jia‐Yin Wang, Ying‐Ying Lei, Jia‐Wang Yuan, Kai Li, Shuang‐Quan Zang","doi":"10.1002/anie.202521059","DOIUrl":"https://doi.org/10.1002/anie.202521059","url":null,"abstract":"Due to their atomically precise structures and tunable electronic properties, coinage metal clusters have emerged as a significant class of luminescent materials, demonstrating broad application potential in the development of optical sensors and light‐emitting diodes. Recently, luminescent coinage metal clusters exhibiting novel photophysical properties, such as afterglow emission, circularly polarized luminescence, near‐infrared luminescence, and x‐ray excited luminescence, have been successively reported, attracting significant research attention. In this work, the first photo‐responsive luminescent silver cluster ( Ag <jats:sub>8</jats:sub> ) was reported, whose phosphorescence can be activated through UV light irradiation in crystal state. Mechanism study revealed that the photo‐response of Ag <jats:sub>8</jats:sub> was attributed to the photo‐induced oxygen scavenging by methanol within the lattice, which relieved the quenching of the phosphorescence of the metal cluster, leading to a “turn‐on” response. Due to its reversible photoactive luminescent properties in the solid state and excellent stability, a specialized photo‐responsive ink for three‐dimensional printing was developed based on Ag <jats:sub>8</jats:sub> . This study expands the range of luminescent coinage metal clusters and offers a novel strategy for the development of coinage metal cluster‐based stimuli‐responsive materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"56 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732012","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}
Pub Date : 2025-12-13DOI: 10.1002/anie.2025-m0512054700
Kateřina Bezděková, Lukáš Severa, Eva Kaletová, Katarina Majerová Varga, Milan Mašát, Liang‐Ting Wu, Jyh‐Chiang Jiang, Ivana Císařová, Jiří Kaleta
{"title":"Outside Front Cover: Surface‐Decoupled Altitudinal and Azimuthal Triptycene‐Fused Tetrapodal Molecular Motors","authors":"Kateřina Bezděková, Lukáš Severa, Eva Kaletová, Katarina Majerová Varga, Milan Mašát, Liang‐Ting Wu, Jyh‐Chiang Jiang, Ivana Císařová, Jiří Kaleta","doi":"10.1002/anie.2025-m0512054700","DOIUrl":"https://doi.org/10.1002/anie.2025-m0512054700","url":null,"abstract":"","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"20 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732013","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}
Pub Date : 2025-12-13DOI: 10.1002/anie.2025-m0512060300
Matteo Damian, Vasilis Tseliou, Patrick Peters, Tanja Knaus, Francesco G. Mutti
{"title":"Outside Back Cover: Amide and Thioester Synthesis Via Oxidative Coupling of Alcohols with Amines or Thiols Using Alcohol Dehydrogenases","authors":"Matteo Damian, Vasilis Tseliou, Patrick Peters, Tanja Knaus, Francesco G. Mutti","doi":"10.1002/anie.2025-m0512060300","DOIUrl":"https://doi.org/10.1002/anie.2025-m0512060300","url":null,"abstract":"","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732041","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}
Rechargeable magnesium batteries (RMBs) have garnered significant attention due to their high energy density, abundant resources, and inherent safety. However, developing cathode materials with both high specific capacity and excellent kinetic performance remains a significant challenge. In this study, two carbonyl‐functionalized covalent organic frameworks (COFs), namely Tp‐DAAQ COF and Tp‐DAA COF, were successfully synthesized via a molecular engineering strategy. Among them, the Tp‐DAAQ COF, with a higher density of carbonyl sites, exhibits superior performance in terms of specific capacity and rate capability. Mechanistic investigations revealed that reversible storage of Mg 2+ is achieved through the enolization reaction of carbonyl groups. Furthermore, molecular dynamics simulations and theoretical calculations indicated that the carbonyl oxygen acts as a negatively charged center, facilitating Mg 2+ dissociation via ion‐dipole interactions and modulating the ion distribution within the COF channels. This significantly reduces the diffusion energy barrier for Mg 2+ within the porous framework. As a result, the Tp‐DAAQ COF cathode exhibits not only a high ion diffusion rate but also exceptional cycling stability, maintaining 72% capacity retention over 4000 cycles at 1000 mA g −1 . This work highlights carbonyl‐rich COFs potential as RMBs cathode, elucidates their high kinetics mechanism, and provides insights into RMBs advanced organic cathode structural design.
可充电镁电池因其能量密度高、资源丰富、安全性好等优点而备受关注。然而，开发既具有高比容量又具有优异动力学性能的正极材料仍然是一个重大挑战。在本研究中，通过分子工程策略成功合成了两个羰基功能化的共价有机框架（COFs），即Tp - DAAQ COF和Tp - DAA COF。其中，Tp - DAAQ COF具有较高的羰基位密度，在比容量和速率能力方面表现出优异的性能。机理研究表明，镁离子的可逆储存是通过羰基烯醇化反应实现的。此外，分子动力学模拟和理论计算表明，羰基氧作为一个带负电荷的中心，通过离子偶极子相互作用促进mg2 +的解离，并调节COF通道内的离子分布。这大大降低了mg2 +在多孔框架内的扩散能垒。因此，Tp - DAAQ COF阴极不仅具有较高的离子扩散率，而且具有优异的循环稳定性，在1000 mA g - 1下，在4000次循环中保持72%的容量保持。本研究突出了富羰基COFs作为RMBs阴极的潜力，阐明了其高动力学机制，并为RMBs高级有机阴极结构设计提供了见解。
{"title":"Molecular Traffic Control: Fast Mg 2+ Transport via Carbonyl‐Induced Ion‐Dipole Interactions in Covalent Organic Framework Channels","authors":"Zhenyu Zhang, Zhimeng Tang, Guangxu Wu, Gaowei Xue, Xiaojin Lian, Hongfei Shi, Xuemin Gan, Hongxing Jia, Baihua Qu, Jingfeng Wang","doi":"10.1002/anie.202524857","DOIUrl":"https://doi.org/10.1002/anie.202524857","url":null,"abstract":"Rechargeable magnesium batteries (RMBs) have garnered significant attention due to their high energy density, abundant resources, and inherent safety. However, developing cathode materials with both high specific capacity and excellent kinetic performance remains a significant challenge. In this study, two carbonyl‐functionalized covalent organic frameworks (COFs), namely Tp‐DAAQ COF and Tp‐DAA COF, were successfully synthesized via a molecular engineering strategy. Among them, the Tp‐DAAQ COF, with a higher density of carbonyl sites, exhibits superior performance in terms of specific capacity and rate capability. Mechanistic investigations revealed that reversible storage of Mg <jats:sup>2+</jats:sup> is achieved through the enolization reaction of carbonyl groups. Furthermore, molecular dynamics simulations and theoretical calculations indicated that the carbonyl oxygen acts as a negatively charged center, facilitating Mg <jats:sup>2+</jats:sup> dissociation via ion‐dipole interactions and modulating the ion distribution within the COF channels. This significantly reduces the diffusion energy barrier for Mg <jats:sup>2+</jats:sup> within the porous framework. As a result, the Tp‐DAAQ COF cathode exhibits not only a high ion diffusion rate but also exceptional cycling stability, maintaining 72% capacity retention over 4000 cycles at 1000 mA g <jats:sup>−1</jats:sup> . This work highlights carbonyl‐rich COFs potential as RMBs cathode, elucidates their high kinetics mechanism, and provides insights into RMBs advanced organic cathode structural design.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731592","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}
Wenpu Fan, Qi Zhang, Xue‐Qing Gong, Yang Lou, Dong Wang
Ceria supported noble metals are important commercial catalysts, however, the long‐term stability suffering from metal particle sintering still challenges the practical benefits. This work determines the favorable migration pathway of supported Pt particles over CeO 2 surface as well as three distinct trends of isomorphous substitution in modulating the metal‐support interactions (MSIs), via extensive ab‐initio molecular dynamics (AIMD) simulations and density functional theory calculations with on‐site Coulomb interaction correction. We find that, while several dopants (Ti, Ge, Sn) enhance the MSI upon contact with metal particles, Ge shows additionally an intriguing MSI weakening effect in the distant region, stemming from the reduction of tetravalence Ge into off‐lattice Ge 2+ cation (Ge 4+ + 2Ce 3+ → Ge 2+ + 2Ce 4+ ). Integrating with the dynamic bury‐and‐expose migratory structure inspires us to propose an effective sintering‐resistance strategy of constructing dual‐stabilization “deeper well and taller wall” migration energetics, simply by manipulating Ge doping content within an estimated threshold (roughly to be one tenth of Pt). Such approach can remarkably stabilize surface Pt particles with migration energy consumption being elevated by 1.80 eV and exhibit broad applicability to other supported metals (e.g., Rh/CeO 2 ), giving rise to excellent stability even under harsh experimental conditions of H 2 atmosphere at 800 °C.
{"title":"Dual‐Stabilization Strategy for Inhibiting Metal Nanoparticle Sintering Over Ceria Surfaces","authors":"Wenpu Fan, Qi Zhang, Xue‐Qing Gong, Yang Lou, Dong Wang","doi":"10.1002/anie.202518312","DOIUrl":"https://doi.org/10.1002/anie.202518312","url":null,"abstract":"Ceria supported noble metals are important commercial catalysts, however, the long‐term stability suffering from metal particle sintering still challenges the practical benefits. This work determines the favorable migration pathway of supported Pt particles over CeO <jats:sub>2</jats:sub> surface as well as three distinct trends of isomorphous substitution in modulating the metal‐support interactions (MSIs), via extensive <jats:italic>ab‐initio</jats:italic> molecular dynamics (AIMD) simulations and density functional theory calculations with on‐site Coulomb interaction correction. We find that, while several dopants (Ti, Ge, Sn) enhance the MSI upon contact with metal particles, Ge shows additionally an intriguing MSI weakening effect in the distant region, stemming from the reduction of tetravalence Ge into off‐lattice Ge <jats:sup>2+</jats:sup> cation (Ge <jats:sup>4+</jats:sup> + 2Ce <jats:sup>3+</jats:sup> → Ge <jats:sup>2+</jats:sup> + 2Ce <jats:sup>4+</jats:sup> ). Integrating with the dynamic bury‐and‐expose migratory structure inspires us to propose an effective sintering‐resistance strategy of constructing dual‐stabilization “deeper well and taller wall” migration energetics, simply by manipulating Ge doping content within an estimated threshold (roughly to be one tenth of Pt). Such approach can remarkably stabilize surface Pt particles with migration energy consumption being elevated by 1.80 eV and exhibit broad applicability to other supported metals (e.g., Rh/CeO <jats:sub>2</jats:sub> ), giving rise to excellent stability even under harsh experimental conditions of H <jats:sub>2</jats:sub> atmosphere at 800 °C.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"93 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731895","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}
Pub Date : 2025-12-13DOI: 10.1002/anie.2025-m0512062000
Jonathan Gutenthaler‐Tietze, Carolina G. Heßler, Lena J. Daumann
{"title":"Inside Back Cover: Influence of Rare Earth Elements on Prebiotic Reaction Networks Resembling the Biologically Relevant Krebs Cycle","authors":"Jonathan Gutenthaler‐Tietze, Carolina G. Heßler, Lena J. Daumann","doi":"10.1002/anie.2025-m0512062000","DOIUrl":"https://doi.org/10.1002/anie.2025-m0512062000","url":null,"abstract":"","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145746676","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}
Zhezhe Li, Suzhen Wang, Yuzhe Ma, Jan C. M. van Hest, Hailong Che
Polymersomes, often referred to as polymeric vesicles, can act as nanoreactors by encapsulating enzymes within their aqueous lumen. However, most polymersome systems exhibit low membrane permeability, hindering substrate exchange and thus posing a critical challenge to their application as nanoreactors. Herein, we report the design of a glutathione (GSH)‐responsive polymersome nanoreactor system with selective intracellular biocatalytic activation. Upon GSH stimulation, the glucose oxidase (GOx)‐loaded polymersome nanoreactors are capable of releasing SO 2 , which enhances the permeability of the polymersome membrane, thereby activating biocatalysis to convert glucose into hydrogen peroxide (H 2 O 2 ). In vitro studies confirmed the successful cellular uptake of nanoreactors, and importantly, the biocatalytic reaction was only activated within cancer cells due to the overexpressed GSH levels, suggesting the system's “ON/OFF” selectivity. Moreover, the GOx‐mediated catalytic reactions, coupled with the concurrent generation of SO 2 , enabled the polymersome nanoreactors to exhibit enhanced cancer cell‐killing capacity by modulating intracellular reactive oxygen species (ROS) levels. This work presents a new strategy for selective biocatalytic activation of nanoreactors, providing a promising platform for the development of functional polymersome systems.
{"title":"Engineering Gas‐Releasing Polymersome Nanoreactors for Selective Biocatalytic Activation","authors":"Zhezhe Li, Suzhen Wang, Yuzhe Ma, Jan C. M. van Hest, Hailong Che","doi":"10.1002/anie.202522097","DOIUrl":"https://doi.org/10.1002/anie.202522097","url":null,"abstract":"Polymersomes, often referred to as polymeric vesicles, can act as nanoreactors by encapsulating enzymes within their aqueous lumen. However, most polymersome systems exhibit low membrane permeability, hindering substrate exchange and thus posing a critical challenge to their application as nanoreactors. Herein, we report the design of a glutathione (GSH)‐responsive polymersome nanoreactor system with selective intracellular biocatalytic activation. Upon GSH stimulation, the glucose oxidase (GOx)‐loaded polymersome nanoreactors are capable of releasing SO <jats:sub>2</jats:sub> , which enhances the permeability of the polymersome membrane, thereby activating biocatalysis to convert glucose into hydrogen peroxide (H <jats:sub>2</jats:sub> O <jats:sub>2</jats:sub> ). In vitro studies confirmed the successful cellular uptake of nanoreactors, and importantly, the biocatalytic reaction was only activated within cancer cells due to the overexpressed GSH levels, suggesting the system's “ON/OFF” selectivity. Moreover, the GOx‐mediated catalytic reactions, coupled with the concurrent generation of SO <jats:sub>2</jats:sub> , enabled the polymersome nanoreactors to exhibit enhanced cancer cell‐killing capacity by modulating intracellular reactive oxygen species (ROS) levels. This work presents a new strategy for selective biocatalytic activation of nanoreactors, providing a promising platform for the development of functional polymersome systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"147 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731590","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}
Xiaokun Zhang, Lingying Zhou, Lingyu Zhang, Deyi Wang, Xiaoyan Zheng, Ning Gao, Guangtao Li
Although coacervates formed via liquid–liquid phase separation (LLPS) are widely considered plausible protocell models relevant to the origin of life, identifying minimalist, ultralow‐molecular‐weight molecules ( Mw <300 Da) capable of undergoing LLPS remains a major challenge. Here we present a class of synthetic phase‐separating molecules with Mw ranging from 211 to 215 Da–among the smallest known to drive coacervation. These molecules feature a modular design comprising a hydrophobic head and a hydrophilic tail, forming a minimalistic framework that significantly reduces molecular freedom and enables precise dissection of the fundamental interactions governing LLPS. Our findings reveal that LLPS is governed by a delicate balance between intermolecular non‐covalent interactions and molecular solvation. Furthermore, this molecular architecture serves as a versatile synthon for modularly constructing a range of task‐specific coacervates, including proton‐responsive, redox‐responsive, light‐responsive, and self‐fluorescent variants. These coacervates selectively accumulate diverse guest molecules and act as efficient bio‐crucibles that support key prebiotic processes, such as amino acid‐involved C─N coupling reactions, chiral catalysis, DNA hybridization, and energy transfer. These results provide both a molecular framework and chemical insights into the minimal requirements for LLPS, while advancing the coacervate toolkit for origins‐of‐life studies and synthetic cell engineering.
{"title":"Minimalist Molecules Drive Liquid–Liquid Phase Separation to Modularly Assemble Functional Coacervate Protocells","authors":"Xiaokun Zhang, Lingying Zhou, Lingyu Zhang, Deyi Wang, Xiaoyan Zheng, Ning Gao, Guangtao Li","doi":"10.1002/anie.202519342","DOIUrl":"https://doi.org/10.1002/anie.202519342","url":null,"abstract":"Although coacervates formed via liquid–liquid phase separation (LLPS) are widely considered plausible protocell models relevant to the origin of life, identifying minimalist, ultralow‐molecular‐weight molecules ( <jats:italic>M</jats:italic> <jats:sub>w</jats:sub> <300 Da) capable of undergoing LLPS remains a major challenge. Here we present a class of synthetic phase‐separating molecules with <jats:italic>M</jats:italic> <jats:sub>w</jats:sub> ranging from 211 to 215 Da–among the smallest known to drive coacervation. These molecules feature a modular design comprising a hydrophobic head and a hydrophilic tail, forming a minimalistic framework that significantly reduces molecular freedom and enables precise dissection of the fundamental interactions governing LLPS. Our findings reveal that LLPS is governed by a delicate balance between intermolecular non‐covalent interactions and molecular solvation. Furthermore, this molecular architecture serves as a versatile synthon for modularly constructing a range of task‐specific coacervates, including proton‐responsive, redox‐responsive, light‐responsive, and self‐fluorescent variants. These coacervates selectively accumulate diverse guest molecules and act as efficient bio‐crucibles that support key prebiotic processes, such as amino acid‐involved C─N coupling reactions, chiral catalysis, DNA hybridization, and energy transfer. These results provide both a molecular framework and chemical insights into the minimal requirements for LLPS, while advancing the coacervate toolkit for origins‐of‐life studies and synthetic cell engineering.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"229 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145731812","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}
Nunzio Matera, Alessio Bussolari, Michele Mancinelli, Roberta Coccia, Nicolò Santarelli, Andrea Pellegrini, Andrea Mazzanti
We report a new class of rationally designed organic photosensitizers based on boron–nitrogen‐substituted scaffolds, capable of mediating challenging triplet energy transfer (EnT) reactions under visible‐light irradiation. Guided by DFT and TD‐DFT calculations, we modulated the twisted intramolecular charge transfer (TICT) character of the excited state through strategic substitution on the carbazole–borane framework, allowing fine‐tuning of both absorption and triplet energy levels ( ET = 63–70 kcal mol −1 ). The most effective catalyst outperformed traditional Ir‐ and xanthone‐based sensitizers across benchmark EnT reactions, including E/Z isomerizations, [2 + 2] photocycloadditions, and [1,3]‐sigmatropic rearrangement. This B–N system enables the sensitization of coumarin‐related substrates with ET ≥ 65 kcal mol −1 , which was previously inaccessible to fully organic EnT photocatalysts. These results establish a new design principle for modular, high‐energy triplet sensitizers based on organic aminoborane scaffolds.
{"title":"Aminoboranes as Rationally Tuned Organic Photosensitizers for Energy Transfer Catalysis","authors":"Nunzio Matera, Alessio Bussolari, Michele Mancinelli, Roberta Coccia, Nicolò Santarelli, Andrea Pellegrini, Andrea Mazzanti","doi":"10.1002/anie.202520339","DOIUrl":"https://doi.org/10.1002/anie.202520339","url":null,"abstract":"We report a new class of rationally designed organic photosensitizers based on boron–nitrogen‐substituted scaffolds, capable of mediating challenging triplet energy transfer (EnT) reactions under visible‐light irradiation. Guided by DFT and TD‐DFT calculations, we modulated the twisted intramolecular charge transfer (TICT) character of the excited state through strategic substitution on the carbazole–borane framework, allowing fine‐tuning of both absorption and triplet energy levels ( <jats:italic>E</jats:italic> <jats:sub>T</jats:sub> = 63–70 kcal mol <jats:sup>−1</jats:sup> ). The most effective catalyst outperformed traditional Ir‐ and xanthone‐based sensitizers across benchmark EnT reactions, including E/Z isomerizations, [2 + 2] photocycloadditions, and [1,3]‐sigmatropic rearrangement. This B–N system enables the sensitization of coumarin‐related substrates with <jats:italic>E</jats:italic> <jats:sub>T</jats:sub> ≥ 65 kcal mol <jats:sup>−1</jats:sup> , which was previously inaccessible to fully organic EnT photocatalysts. These results establish a new design principle for modular, high‐energy triplet sensitizers based on organic aminoborane scaffolds.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"15 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732044","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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