Jorge Pascual,Marion Flatken,Eros Radicchi,Mahmoud Aldamasy,Shuaifeng Hu,Omar E Solis,Silver-Hamill Turren-Cruz,Guixiang Li,Armin Hoell,Susan Schorr,Meng Li,Filippo De Angelis,Artem Musiienko,André Dallmann,Antonio Abate
Narrow-bandgap tin and mixed tin-lead halide perovskites are attracting growing interest for optoelectronic applications, yet the difficult-to-control crystallization process has hindered their development. Although additive engineering has effectively improved film formation, the fundamental origins of their distinct crystallization behavior remain less explored. Here, through direct comparison with Pb counterparts, we investigate the pre-crystallization stages of Sn-based perovskite precursor solutions through complementary structural characterizations. We show that Sn precursors are intrinsically more reactive and sensitive to their chemical environment, exhibiting poorer colloidal stability compared to Pb and a strong inherent tendency to agglomerate. These findings explain their narrower processing window, where small variations in solution chemistry strongly affect nucleation and crystallization dynamics. To fabricate high-quality tin-based perovskite through solution methods, we highlight the importance of controlling the often-overlooked pre-crystallization stages, though, for example, rational solvent and additive designs. Overall, we provide fundamental insights into precursor solution chemistry and establish pre-crystallization engineering as a key strategy for overcoming long-standing limitations in thin-film fabrication, particularly in light of the field's rapid progression toward large-scale, sustainable, and solvent-conscious manufacturing.
{"title":"Unravelling the Intrinsic Reactivity and Colloidal Instability in Tin-Based Halide Perovskite Precursor Solutions.","authors":"Jorge Pascual,Marion Flatken,Eros Radicchi,Mahmoud Aldamasy,Shuaifeng Hu,Omar E Solis,Silver-Hamill Turren-Cruz,Guixiang Li,Armin Hoell,Susan Schorr,Meng Li,Filippo De Angelis,Artem Musiienko,André Dallmann,Antonio Abate","doi":"10.1002/anie.7703450","DOIUrl":"https://doi.org/10.1002/anie.7703450","url":null,"abstract":"Narrow-bandgap tin and mixed tin-lead halide perovskites are attracting growing interest for optoelectronic applications, yet the difficult-to-control crystallization process has hindered their development. Although additive engineering has effectively improved film formation, the fundamental origins of their distinct crystallization behavior remain less explored. Here, through direct comparison with Pb counterparts, we investigate the pre-crystallization stages of Sn-based perovskite precursor solutions through complementary structural characterizations. We show that Sn precursors are intrinsically more reactive and sensitive to their chemical environment, exhibiting poorer colloidal stability compared to Pb and a strong inherent tendency to agglomerate. These findings explain their narrower processing window, where small variations in solution chemistry strongly affect nucleation and crystallization dynamics. To fabricate high-quality tin-based perovskite through solution methods, we highlight the importance of controlling the often-overlooked pre-crystallization stages, though, for example, rational solvent and additive designs. Overall, we provide fundamental insights into precursor solution chemistry and establish pre-crystallization engineering as a key strategy for overcoming long-standing limitations in thin-film fabrication, particularly in light of the field's rapid progression toward large-scale, sustainable, and solvent-conscious manufacturing.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"190 1","pages":"e7703450"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502380","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}
{"title":"Correction to \"Defect-Rich Adhesive Nanozymes as Efficient Antibiotics for Enhanced Bacterial Inhibition\".","authors":"","doi":"10.1002/anie.7386489","DOIUrl":"https://doi.org/10.1002/anie.7386489","url":null,"abstract":"","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":"e7386489"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502485","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}
Integrating achiral luminophores into chiral supramolecular helices represents a promising route to strong circularly polarized luminescence (CPL). However, for lanthanide systems, efficient emitter loading and effective chirality induction remain challenging due to weak host-guest interactions and the shielded nature of 4f electrons. Herein, we report a supramolecular chelation strategy that implants Eu3+ emitters into pre‑assembled helical nanoribbons (HNRs), enabling efficient chirality induction and tunable CPL brightness. Two cholesterol-terpyridine conjugates, differing only in their linker chemistry (ester vs. carbonate), demonstrate that the ester linker promotes long‑range chirality induction and HNR formation, whereas the carbonate counterpart yields achiral aggregates. Moreover, the assembly sequence is crucial: pre‑formation of the helical scaffold preserves the non‑covalent network necessary for effective chirality induction, whereas prior metal coordination introduces steric hindrance that disrupts chiral order. The resulting systems exhibit orthogonal luminescence responses: Eu3+‑loaded assemblies are humidity‑sensitive but thermally stable, while β‑diketonate‑shielded analogues are temperature‑responsive yet humidity‑resistant, allowing multi‑level information encryption. By introducing this modular "assemble‑then‑coordinate" approach, we provide new insights into supramolecular chirality induction and open avenues toward advanced, stimulus‑responsive CPL materials.
{"title":"Implanting Lanthanide Luminophores Into Helical Scaffolds for Programmable Circularly Polarized Luminescence.","authors":"Fu-Jia Song,Kai Wang,Xiang-Yuan Yan,Kai Cui,Nan Song,Xuefeng Zhu,Chun-Hua Yan,Pingru Su,Yu Tang","doi":"10.1002/anie.9901177","DOIUrl":"https://doi.org/10.1002/anie.9901177","url":null,"abstract":"Integrating achiral luminophores into chiral supramolecular helices represents a promising route to strong circularly polarized luminescence (CPL). However, for lanthanide systems, efficient emitter loading and effective chirality induction remain challenging due to weak host-guest interactions and the shielded nature of 4f electrons. Herein, we report a supramolecular chelation strategy that implants Eu3+ emitters into pre‑assembled helical nanoribbons (HNRs), enabling efficient chirality induction and tunable CPL brightness. Two cholesterol-terpyridine conjugates, differing only in their linker chemistry (ester vs. carbonate), demonstrate that the ester linker promotes long‑range chirality induction and HNR formation, whereas the carbonate counterpart yields achiral aggregates. Moreover, the assembly sequence is crucial: pre‑formation of the helical scaffold preserves the non‑covalent network necessary for effective chirality induction, whereas prior metal coordination introduces steric hindrance that disrupts chiral order. The resulting systems exhibit orthogonal luminescence responses: Eu3+‑loaded assemblies are humidity‑sensitive but thermally stable, while β‑diketonate‑shielded analogues are temperature‑responsive yet humidity‑resistant, allowing multi‑level information encryption. By introducing this modular \"assemble‑then‑coordinate\" approach, we provide new insights into supramolecular chirality induction and open avenues toward advanced, stimulus‑responsive CPL materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"306 1","pages":"e9901177"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502498","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}
Solution-processed scintillators exhibiting long-lasting radioluminescence upon X-ray irradiation hold great promise for flexible and high-resolution X-ray imaging. However, their practical implementation is typically impeded by deep electronic traps that require thermally stimulated readout at high temperature to release stored charges, leading to image ghosting and limited recyclability. Here, we report Cs2ZrCl6:Te4+ perovskite scintillators featuring X-ray-induced Frenkel defect-associated shallow traps that enable long-lasting radioluminescence at room temperature. Spectroscopic and theoretical studies reveal that X-ray irradiation generates shallow electron-hole traps, which facilitate efficient charge capture and thermal release, producing persistent luminescence under ambient conditions. Te4+ doping optimizes the defect landscape, stabilizing shallow traps and promoting favorable charge trapping-detrapping dynamics. By embedding these microcrystals into a flexible PDMS matrix, we fabricate a scintillating film capable of high-resolution, ghosting-free, time-lapse X-ray imaging with a spatial resolution of 18.5 lp mm-1 and recyclable imaging performance. This study highlights the potential of shallow-trap perovskite scintillators for next-generation flexible X-ray imaging technologies.
{"title":"Shallow-Trap Perovskite Scintillators for High-Resolution, Ghosting-Free X-Ray Imaging.","authors":"Weihong Li,Yao Yao,Libin Zheng,Xiaoze Wang,Shuheng Dai,Xiaoling Chen,Zhijian Yang,Qinxia Wu,Lili Xie,Xiaofeng Chen,Zhenzhen Zhang,Huanghao Yang,Qiushui Chen","doi":"10.1002/anie.4716874","DOIUrl":"https://doi.org/10.1002/anie.4716874","url":null,"abstract":"Solution-processed scintillators exhibiting long-lasting radioluminescence upon X-ray irradiation hold great promise for flexible and high-resolution X-ray imaging. However, their practical implementation is typically impeded by deep electronic traps that require thermally stimulated readout at high temperature to release stored charges, leading to image ghosting and limited recyclability. Here, we report Cs2ZrCl6:Te4+ perovskite scintillators featuring X-ray-induced Frenkel defect-associated shallow traps that enable long-lasting radioluminescence at room temperature. Spectroscopic and theoretical studies reveal that X-ray irradiation generates shallow electron-hole traps, which facilitate efficient charge capture and thermal release, producing persistent luminescence under ambient conditions. Te4+ doping optimizes the defect landscape, stabilizing shallow traps and promoting favorable charge trapping-detrapping dynamics. By embedding these microcrystals into a flexible PDMS matrix, we fabricate a scintillating film capable of high-resolution, ghosting-free, time-lapse X-ray imaging with a spatial resolution of 18.5 lp mm-1 and recyclable imaging performance. This study highlights the potential of shallow-trap perovskite scintillators for next-generation flexible X-ray imaging technologies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"22 1","pages":"e4716874"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495173","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}
Zhongyun Liu,Yuhe Cao,Ryan P Lively,William J Koros
Helium/methane (He/CH4) separation is of strategic importance for energy and industrial applications, yet it remains technically challenging due to the need to simultaneously achieve ultrahigh selectivity and helium productivity. In this work, we report ultraselective Matrimid-derived asymmetric carbon molecular sieve (CMS) hollow fibers in which ultramicropore and fiber geometry are deliberately co-engineered to enable precise He/CH4 separation with high He productivity at the module level. We showed that pyrolysis temperature tuning tightens ångström-scale ultramicropores and enhances He/CH4 discrimination; while a targeted post-pyrolysis hyperaging enables selective refining of the ultramicropores, thereby offering high He permeance with exceptional He/CH4 selectivity. For a 5/95 He/CH4 mixed gas feed, the hyperaged CMS-700 hollow fibers achieve permeate helium purities of up to 98.6% with He/CH4 selectivities exceeding 1300 and a stable He permeance of approximately 26 GPU. Beyond this material achievement, fiber geometry optimization through reduction of the outer diameter was achieved to increase the packable membrane area without compromising mechanical integrity or intrinsic separation performance, leading to enhanced module-level He productivity. This integrated co-engineering strategy provides an energy-efficient and industrially viable platform for He recovery and is readily extendable to other challenging small/large gas-pair separations.
{"title":"Matrimid-Derived Asymmetric Carbon Molecular Sieve Hollow Fibers With Engineered Ultramicropores for Precise Helium Separation.","authors":"Zhongyun Liu,Yuhe Cao,Ryan P Lively,William J Koros","doi":"10.1002/anie.6271309","DOIUrl":"https://doi.org/10.1002/anie.6271309","url":null,"abstract":"Helium/methane (He/CH4) separation is of strategic importance for energy and industrial applications, yet it remains technically challenging due to the need to simultaneously achieve ultrahigh selectivity and helium productivity. In this work, we report ultraselective Matrimid-derived asymmetric carbon molecular sieve (CMS) hollow fibers in which ultramicropore and fiber geometry are deliberately co-engineered to enable precise He/CH4 separation with high He productivity at the module level. We showed that pyrolysis temperature tuning tightens ångström-scale ultramicropores and enhances He/CH4 discrimination; while a targeted post-pyrolysis hyperaging enables selective refining of the ultramicropores, thereby offering high He permeance with exceptional He/CH4 selectivity. For a 5/95 He/CH4 mixed gas feed, the hyperaged CMS-700 hollow fibers achieve permeate helium purities of up to 98.6% with He/CH4 selectivities exceeding 1300 and a stable He permeance of approximately 26 GPU. Beyond this material achievement, fiber geometry optimization through reduction of the outer diameter was achieved to increase the packable membrane area without compromising mechanical integrity or intrinsic separation performance, leading to enhanced module-level He productivity. This integrated co-engineering strategy provides an energy-efficient and industrially viable platform for He recovery and is readily extendable to other challenging small/large gas-pair separations.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":"e6271309"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502382","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}
In biological systems, certain fundamental biomacromolecules, such as proteins and DNA, fulfill specific biological functions via structural changes triggered by stimuli. Herein, we report the synthesis of two allosteric regulation metal-organic octahedra (S1 and S2) with tailored cavities/windows. Both cages exhibit distinct aggregation-induced emission (AIE) colors and quantum yields. Single-crystal x-ray diffraction reveals that S2, featuring longer arms, adopts a denser π-stacking arrangement, rationalizing its superior emissive properties. The kinetically driven multicomponent heteroleptic octahedral mixtures formed under ambient temperature assembly conditions transformed into self-sorted S1 and S2 upon heating. The addition of competitive building blocks enabled the transformation from S1 to S2. Notably, 365 nm light irradiation induces planarization of the COT units, driving a rapid structural transformation from three-dimensional (3D) octahedra to two-dimensional (2D) metal-organic nanosheets (NS-1 and NS-2) within minutes. This work provides a novel approach for designing responsive systems and demonstrates broad potential applications in areas such as optoelectronics, targeted delivery, and smart materials.
{"title":"Cyclooctatetraenyl Metal-Organic Octahedra and Their 3D Cage to 2D Nanosheet Transformations.","authors":"Ning Wang,Yijun Xiao,Die Liu,Wei-Dong Yu,Jun Wang,Wanying Zhong,Fan Fu,Fengxue Liu,Ting-Zheng Xie,Peiyang Su,Zhilong Jiang,Pingshan Wang,Mingzhao Chen","doi":"10.1002/anie.4205687","DOIUrl":"https://doi.org/10.1002/anie.4205687","url":null,"abstract":"In biological systems, certain fundamental biomacromolecules, such as proteins and DNA, fulfill specific biological functions via structural changes triggered by stimuli. Herein, we report the synthesis of two allosteric regulation metal-organic octahedra (S1 and S2) with tailored cavities/windows. Both cages exhibit distinct aggregation-induced emission (AIE) colors and quantum yields. Single-crystal x-ray diffraction reveals that S2, featuring longer arms, adopts a denser π-stacking arrangement, rationalizing its superior emissive properties. The kinetically driven multicomponent heteroleptic octahedral mixtures formed under ambient temperature assembly conditions transformed into self-sorted S1 and S2 upon heating. The addition of competitive building blocks enabled the transformation from S1 to S2. Notably, 365 nm light irradiation induces planarization of the COT units, driving a rapid structural transformation from three-dimensional (3D) octahedra to two-dimensional (2D) metal-organic nanosheets (NS-1 and NS-2) within minutes. This work provides a novel approach for designing responsive systems and demonstrates broad potential applications in areas such as optoelectronics, targeted delivery, and smart materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"146 1","pages":"e4205687"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495184","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}
Achieving highly selective molecular recognition in the solid state remains a major challenge in supramolecular chemistry. Herein, we introduce a molecular-gate strategy that dynamically amplifies intrinsic solid-state recognition selectivity in a macrocyclic host-guest system. A perethylated leaning pillar[6]arene (EtLP6) accommodates both 1,3- and 1,4-dioxane isomers in the solid state, exhibiting only modest inherent selectivity. Remarkably, incorporation of an independent, reversible, charge-transfer-active molecular gate, tetrafluoroterephthalonitrile (TFTN), converts this weak preference into highly selective recognition through competitive binding and solid-state reorganization. The stronger-binding 1,4-dioxane displaces TFTN to open the gate and form a host-guest complex, whereas the weaker-binding 1,3-dioxane stabilizes a gated CT assembly that suppresses complexation. This gate-controlled process couples selective recognition with switchable CT interactions, enabling vapochromic discrimination of dioxane isomers. Furthermore, sequential competitive binding enables dynamic regulation of solid-state assemblies, including room-temperature-controlled guest release, and host recyclability. This work establishes molecular gating as a general and conceptually simple strategy for regulating selectivity and functionality in solid-state macrocyclic host-guest systems.
{"title":"Molecular-Gate Strategy for Solid-State Selective Recognition of Dioxane Isomers via Reversible Host-Guest and Charge-Transfer Modulation.","authors":"Yuan-Zheng Liu,Yu-Xiang Sun,Susu Ren,Xiang-Shuai Li,Haitao Wang,Jia-Rui Wu","doi":"10.1002/anie.3482686","DOIUrl":"https://doi.org/10.1002/anie.3482686","url":null,"abstract":"Achieving highly selective molecular recognition in the solid state remains a major challenge in supramolecular chemistry. Herein, we introduce a molecular-gate strategy that dynamically amplifies intrinsic solid-state recognition selectivity in a macrocyclic host-guest system. A perethylated leaning pillar[6]arene (EtLP6) accommodates both 1,3- and 1,4-dioxane isomers in the solid state, exhibiting only modest inherent selectivity. Remarkably, incorporation of an independent, reversible, charge-transfer-active molecular gate, tetrafluoroterephthalonitrile (TFTN), converts this weak preference into highly selective recognition through competitive binding and solid-state reorganization. The stronger-binding 1,4-dioxane displaces TFTN to open the gate and form a host-guest complex, whereas the weaker-binding 1,3-dioxane stabilizes a gated CT assembly that suppresses complexation. This gate-controlled process couples selective recognition with switchable CT interactions, enabling vapochromic discrimination of dioxane isomers. Furthermore, sequential competitive binding enables dynamic regulation of solid-state assemblies, including room-temperature-controlled guest release, and host recyclability. This work establishes molecular gating as a general and conceptually simple strategy for regulating selectivity and functionality in solid-state macrocyclic host-guest systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"28 1","pages":"e3482686"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147495174","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}
Acetal[6]arenes (Ac[6]) are introduced as a new class of rigid chiral macrocyclic arenes in which carbon-centered chirality is embedded in a trioxabicyclo[3.3.1]nonane motif at macrocyclic waist. Ac[6] efficiently forms charge-transfer (CT) complexes with electron-deficient aromatic guests in both solution and the solid state. Single-crystal x-ray diffraction reveals that guest molecules bind to the outer surface of Ac[6] through well-defined stacking interactions. In contrast, the corresponding acyclic bis-acetal precursors show no complexation behavior, indicating that the rigid macrocyclic topology suppresses ring-unit flipping and significantly enhances interfacial π-π interactions. The resulting solid-state complexes exhibit dual emission at CT band (prompt fluorescence and TADF). Notably, complexes derived from enantiopure Ac[6] display intense circular dichroism (CD) and circularly polarized luminescence (CPL). The associated dissymmetry factors (gabs and glum) even exceed intrinsic Ac[6] values, indicating highly efficient chiral transfer. Ac[6] shows robust guest-capture capability, forming CT complexes not only via solution co-crystallization but also through simple physical mixing and even gas-phase guest uptake. By exploiting time-dependent capture kinetics and multicolor optoelectronic properties, we developed applications for optical sensing and time-encoded encryption. These results establish macrocyclization of rigid chirality-on-annulus units as a powerful strategy for creating functional supramolecular CT materials with emergent chiroptical and optoelectronic properties.
{"title":"Acetal[6]Arenes: Rigid Chirality-on-Annulus Macrocycles Promoting Charge-Transfer Co-Assembly With Exceptional (Chiro)Optical Properties.","authors":"Lizhi Fang,Long Chen,Yimin Zhu,Xue Li,Jiecheng Ji,Xiaotong Liang,Pinyou Wang,Dayang Zhou,Xiaochuan Chen,Wanhua Wu,Cheng Yang","doi":"10.1002/anie.4969685","DOIUrl":"https://doi.org/10.1002/anie.4969685","url":null,"abstract":"Acetal[6]arenes (Ac[6]) are introduced as a new class of rigid chiral macrocyclic arenes in which carbon-centered chirality is embedded in a trioxabicyclo[3.3.1]nonane motif at macrocyclic waist. Ac[6] efficiently forms charge-transfer (CT) complexes with electron-deficient aromatic guests in both solution and the solid state. Single-crystal x-ray diffraction reveals that guest molecules bind to the outer surface of Ac[6] through well-defined stacking interactions. In contrast, the corresponding acyclic bis-acetal precursors show no complexation behavior, indicating that the rigid macrocyclic topology suppresses ring-unit flipping and significantly enhances interfacial π-π interactions. The resulting solid-state complexes exhibit dual emission at CT band (prompt fluorescence and TADF). Notably, complexes derived from enantiopure Ac[6] display intense circular dichroism (CD) and circularly polarized luminescence (CPL). The associated dissymmetry factors (gabs and glum) even exceed intrinsic Ac[6] values, indicating highly efficient chiral transfer. Ac[6] shows robust guest-capture capability, forming CT complexes not only via solution co-crystallization but also through simple physical mixing and even gas-phase guest uptake. By exploiting time-dependent capture kinetics and multicolor optoelectronic properties, we developed applications for optical sensing and time-encoded encryption. These results establish macrocyclization of rigid chirality-on-annulus units as a powerful strategy for creating functional supramolecular CT materials with emergent chiroptical and optoelectronic properties.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":"e4969685"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502381","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}
Catalytic decarboxylative allylic alkylation (DAA) reaction represents an efficient strategy for synthesizing molecules containing both carbonyl and alkenyl functionalities, yet is frequently challenged by multiple selectivity issues. Here we report the first intermolecular decarboxylative cross-coupling of β-ketoacids with internal allenes. Using a Rh(I)/(S,S)-Ph-BPE system, α-gem-difluoroallylic carbonyl compounds can be generated with excellent chemo-, regio-, and enantioselectivities. Mechanistic studies support "coordination-assisted inner-sphere addition-decarboxylation" pathway, where C─C bond formation occurs prior to the decarboxylation step. Fluorine-induced anti→syn isomerization of π-allyl-rhodium species proves to be the key factor governing the stereoselectivity of this reaction. This cross-coupling reaction tolerates a range of functional groups and advances the field of decarboxylative allylic alkylation.
{"title":"Catalytic Enantioselective Decarboxylative Cross-Coupling of β-Ketoacids With gem-Difluoroallenes Enabled by Fluorine-Induced Allylrhodium Isomerization.","authors":"Hong-Song Shi,Yi-Dan Miao,Xiaodong Tang,Heng-Ying Xiong,Jing Nie,Yanfeng Dang,Jun-An Ma,Fa-Guang Zhang","doi":"10.1002/anie.4973244","DOIUrl":"https://doi.org/10.1002/anie.4973244","url":null,"abstract":"Catalytic decarboxylative allylic alkylation (DAA) reaction represents an efficient strategy for synthesizing molecules containing both carbonyl and alkenyl functionalities, yet is frequently challenged by multiple selectivity issues. Here we report the first intermolecular decarboxylative cross-coupling of β-ketoacids with internal allenes. Using a Rh(I)/(S,S)-Ph-BPE system, α-gem-difluoroallylic carbonyl compounds can be generated with excellent chemo-, regio-, and enantioselectivities. Mechanistic studies support \"coordination-assisted inner-sphere addition-decarboxylation\" pathway, where C─C bond formation occurs prior to the decarboxylation step. Fluorine-induced anti→syn isomerization of π-allyl-rhodium species proves to be the key factor governing the stereoselectivity of this reaction. This cross-coupling reaction tolerates a range of functional groups and advances the field of decarboxylative allylic alkylation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"15 1","pages":"e4973244"},"PeriodicalIF":16.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502376","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}
Achieving efficient solar-to-hydrogen (STH) conversion is essential for renewable energy storage, yet solar-driven water splitting remains fundamentally limited by energy losses associated with the anodic oxygen evolution reaction (OER). Herein, we deliberately combine Ir species with a NiFe model electrocatalyst to construct asymmetric Ir-O-Ni interfacial sites that optimize anodic reaction energetics. In situ spectroscopic analyses combined with theoretical calculations reveal that, in contrast to pristine NiFe operating via the conventional adsorbate evolution mechanism, the Ir-O-Ni interfacial sites directly participate in OER by lowering the *OOH deprotonation barrier and facilitating rapid proton transfer under alkaline conditions. Meanwhile, strong Ir-O orbital coupling stabilizes O-containing intermediates, thereby reducing the O-O bond formation barrier from 3.21 eV in pristine NiFe to 1.40 eV in NiFe-Ir. Consequently, NiFe-Ir delivers a low overpotential of 300 mV at a high current density of 500 mA cm-2, corresponding to a 43.3% reduction in energy consumption compared to NiFe (430 mV). Importantly, the substantially reduced anodic energy dissipation translates directly into enhanced device-level performance, enabling the integrated photovoltaic-electrolyzer system to achieve an exceptional STH conversion efficiency of 19.7%. These results underscore interfacial engineering as a powerful and generalizable strategy for advancing practical solar water-splitting technologies.
实现高效的太阳能制氢（STH）转换对于可再生能源储存至关重要，但太阳能驱动的水分解仍然受到与阳极析氧反应（OER）相关的能量损失的限制。本文中，我们故意将Ir物种与NiFe模型电催化剂结合，构建了不对称的Ir- o - ni界面位点，优化了阳极反应的能量。原位光谱分析结合理论计算表明，与原始NiFe通过传统吸附物演化机制运行相比，Ir-O-Ni界面位点通过降低*OOH去质子化势垒和促进碱性条件下的快速质子转移直接参与OER。同时，强的Ir-O轨道耦合稳定了含o的中间体，从而将O-O键形成势垒从原始NiFe中的3.21 eV降低到NiFe- ir中的1.40 eV。因此，NiFe- ir在500 mA cm-2的高电流密度下提供300 mV的低过电位，与NiFe （430 mV）相比，能耗降低43.3%。重要的是，大大降低的阳极能量耗散直接转化为器件级性能的增强，使集成光伏-电解槽系统能够实现19.7%的特殊STH转换效率。这些结果强调了界面工程作为一种强大的、可推广的策略来推进实用的太阳能水分解技术。
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