Pub Date : 2026-03-16DOI: 10.1016/j.chempr.2026.102943
Thomas W. Colburn, Abigail Carbone, Justus Just, Sarah Bindon, Ryan Wainer, Robert D. Miller, Reinhold H. Dauskardt
Solution combustion synthesis (SCS) is a rapid and scalable synthetic pathway for producing metallic and oxide nanoparticles and thin films, resulting from the exothermic combustion between a metal cation, chelating organic fuel, and an oxidant. However, understanding the divergence in SCS between thin-film and unconfined bulk combustion, as well as in situ experiments probing the reaction progression, remains limited. Here, we leverage X-ray absorption spectroscopy (XAS), along with other X-ray- and electron-based characterizations, to explore the interplay between precursor chemistry and combustion geometry (thin film versus bulk powder) in yielding a range of nickel-based oxide, metallic, and complex carbide/metallic structures, with generalizability to other transition metals. We develop a fundamental understanding of the effect of precursor stoichiometries on the reaction products attainable using SCS. Using shallow-angle in situ XAS, we then measure the kinetics and activation energies for thin-film conversion via combustion synthesis.
{"title":"In situ insights from non-equilibrium solution combustion synthesis: From semiconducting thin films to metallic nanostructures","authors":"Thomas W. Colburn, Abigail Carbone, Justus Just, Sarah Bindon, Ryan Wainer, Robert D. Miller, Reinhold H. Dauskardt","doi":"10.1016/j.chempr.2026.102943","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102943","url":null,"abstract":"Solution combustion synthesis (SCS) is a rapid and scalable synthetic pathway for producing metallic and oxide nanoparticles and thin films, resulting from the exothermic combustion between a metal cation, chelating organic fuel, and an oxidant. However, understanding the divergence in SCS between thin-film and unconfined bulk combustion, as well as <em>in situ</em> experiments probing the reaction progression, remains limited. Here, we leverage X-ray absorption spectroscopy (XAS), along with other X-ray- and electron-based characterizations, to explore the interplay between precursor chemistry and combustion geometry (thin film versus bulk powder) in yielding a range of nickel-based oxide, metallic, and complex carbide/metallic structures, with generalizability to other transition metals. We develop a fundamental understanding of the effect of precursor stoichiometries on the reaction products attainable using SCS. Using shallow-angle <em>in situ</em> XAS, we then measure the kinetics and activation energies for thin-film conversion via combustion synthesis.","PeriodicalId":268,"journal":{"name":"Chem","volume":"20 1","pages":"102943"},"PeriodicalIF":23.5,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478925","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 : 2026-03-16DOI: 10.1016/j.chempr.2026.102947
Tom Bösking, Denise Schwarz, Daniel Aßenmacher, Oliver Fiukowski, Michael Pohl, Mike Pauls, Christoph Bannwarth, Dušan Kolarski, Stefan Hecht
Chemists utilize cyclic constraints in molecules to control conformation, shape, and reactivity. The strain introduced in the (macro)cycles is released during reactions and drives transformations ranging from strain-promoted in vivo ligation to ring-opening metathesis polymerization. However, in each case, the ring size needs careful optimization and cannot be (re)adjusted. For remote optical modulation of strain, we designed looped diarylethene photoswitches that undergo reversible ring contraction/expansion upon electrocyclic ring closure/opening. Investigating a homologous series, we discovered that the long-wavelength absorption of the closed isomer serves as a diagnostic tool for stored molecular strain. By incorporating an internal allene reactive group in the loop, we enhanced its reactivity in a [3+2] dipolar cycloaddition with ethyl diazoacetate under visible light. Quantum chemical calculations helped rationalize the experimentally observed size-dependent photochemistry and reactivity of the macrocycles. Our approach opens opportunities for optical spatiotemporal reactivity control in life and materials science applications.
{"title":"Light-driven reversible ring contraction and expansion to modulate strain, conformation, and reactivity","authors":"Tom Bösking, Denise Schwarz, Daniel Aßenmacher, Oliver Fiukowski, Michael Pohl, Mike Pauls, Christoph Bannwarth, Dušan Kolarski, Stefan Hecht","doi":"10.1016/j.chempr.2026.102947","DOIUrl":"https://doi.org/10.1016/j.chempr.2026.102947","url":null,"abstract":"Chemists utilize cyclic constraints in molecules to control conformation, shape, and reactivity. The strain introduced in the (macro)cycles is released during reactions and drives transformations ranging from strain-promoted <em>in vivo</em> ligation to ring-opening metathesis polymerization. However, in each case, the ring size needs careful optimization and cannot be (re)adjusted. For remote optical modulation of strain, we designed looped diarylethene photoswitches that undergo reversible ring contraction/expansion upon electrocyclic ring closure/opening. Investigating a homologous series, we discovered that the long-wavelength absorption of the closed isomer serves as a diagnostic tool for stored molecular strain. By incorporating an internal allene reactive group in the loop, we enhanced its reactivity in a [3+2] dipolar cycloaddition with ethyl diazoacetate under visible light. Quantum chemical calculations helped rationalize the experimentally observed size-dependent photochemistry and reactivity of the macrocycles. Our approach opens opportunities for optical spatiotemporal reactivity control in life and materials science applications.","PeriodicalId":268,"journal":{"name":"Chem","volume":"13 1","pages":"102947"},"PeriodicalIF":23.5,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490076","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 : 2026-03-12Epub Date: 2026-02-04DOI: 10.1016/j.chempr.2025.102877
Lida Vadakumchery , Christoph M. Meier , Clarissa C. Forneris , Lucas Paoli , Alicia Courvoisier-Clément , Agneya Bhushan , Alessandro Lotti , Chandrashekhar Padhi , Shinichi Sunagawa , Alvar D. Gossert , Jörn Piel
Polytheonamides are extraordinarily complex and potent ribosomal peptide cytotoxins featuring up to 50 mostly non-canonical post-translational modifications, including 18 d-amino acids. They act by forming minimalistic, unimolecular transmembrane ion channels that adopt a β-helical structure. Only a few related natural products are known, and they occur mostly in uncultivated, poorly studied bacteria. Here, we report the genomic discovery of a large, cryptic peptide family, termed origamins, that occurs in phylogenetically diverse, well-known bacteria, including Escherichia coli. Characterization of several pathways revealed striking similarities to polytheonamides, indicating convergent evolution of the complex maturation pattern. These include up to 44 modifications, a β-helical structure, and cytotoxic activity. A high prevalence in human-associated bacteria, including symbionts and pathogens, suggests widespread roles in host-microbiome interactions.
{"title":"Widespread hypermodified β-helical peptides in common bacteria","authors":"Lida Vadakumchery , Christoph M. Meier , Clarissa C. Forneris , Lucas Paoli , Alicia Courvoisier-Clément , Agneya Bhushan , Alessandro Lotti , Chandrashekhar Padhi , Shinichi Sunagawa , Alvar D. Gossert , Jörn Piel","doi":"10.1016/j.chempr.2025.102877","DOIUrl":"10.1016/j.chempr.2025.102877","url":null,"abstract":"<div><div>Polytheonamides are extraordinarily complex and potent ribosomal peptide cytotoxins featuring up to 50 mostly non-canonical post-translational modifications, including 18 <span>d</span>-amino acids. They act by forming minimalistic, unimolecular transmembrane ion channels that adopt a β-helical structure. Only a few related natural products are known, and they occur mostly in uncultivated, poorly studied bacteria. Here, we report the genomic discovery of a large, cryptic peptide family, termed origamins, that occurs in phylogenetically diverse, well-known bacteria, including <em>Escherichia coli</em>. Characterization of several pathways revealed striking similarities to polytheonamides, indicating convergent evolution of the complex maturation pattern. These include up to 44 modifications, a β-helical structure, and cytotoxic activity. A high prevalence in human-associated bacteria, including symbionts and pathogens, suggests widespread roles in host-microbiome interactions.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 3","pages":"Article 102877"},"PeriodicalIF":19.6,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147428979","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 : 2026-03-12Epub Date: 2025-10-01DOI: 10.1016/j.chempr.2025.102750
Jiamin Ye , Yueyue Fan , Gaoli Niu , Yong Kang , Jiacheng Shi , Ruiyan Li , Yiwen Yang , Xiaoyuan Ji
Colorectal cancer (CRC) remains a major global health challenge due to insufficient tumor penetration and immunosuppressive microenvironments. Herein, we propose a modular train-style nanorobot (TPP-Exo@LOX-Pd-Cu7S4) as a targeted synergistic therapeutic platform for CRC. The exosome “head” enables neutrophil-like tumor homing, while the Cu7S4 “tail” generates thermophoretic propulsion for deep tumor penetration. Under near-infrared region II (NIR-II) laser irradiation, the Pd-Cu7S4 Schottky heterojunction drives highly efficient catalytic cascades, disrupting redox homeostasis and inducing metabolic stress by converting O₂ to ·O₂−, H₂O₂ to ·OH, GSH to GSSG, NADH to NAD+, and lactate to pyruvate. The nanorobot directly targets mitochondria to reprogram tumor metabolism and trigger cuproptosis. Meanwhile, lactate oxidase (LOX), encapsulated within the engineered exosomes, depletes excess lactate to relieve immunosuppression and boost antitumor immunity. In CRC models, these nanorobots exhibit strong barrier penetration, precise targeting, and deep tumor infiltration, offering a multifunctional and metabolically disruptive therapeutic approach.
{"title":"Modular train-style nanorobots for targeted deep penetration and multi-directional collaborative treatment of colorectal cancer","authors":"Jiamin Ye , Yueyue Fan , Gaoli Niu , Yong Kang , Jiacheng Shi , Ruiyan Li , Yiwen Yang , Xiaoyuan Ji","doi":"10.1016/j.chempr.2025.102750","DOIUrl":"10.1016/j.chempr.2025.102750","url":null,"abstract":"<div><div>Colorectal cancer (CRC) remains a major global health challenge due to insufficient tumor penetration and immunosuppressive microenvironments. Herein, we propose a modular train-style nanorobot (TPP-Exo@LOX-Pd-Cu<sub>7</sub>S<sub>4</sub>) as a targeted synergistic therapeutic platform for CRC. The exosome “head” enables neutrophil-like tumor homing, while the Cu<sub>7</sub>S<sub>4</sub> “tail” generates thermophoretic propulsion for deep tumor penetration. Under near-infrared region II (NIR-II) laser irradiation, the Pd-Cu<sub>7</sub>S<sub>4</sub> Schottky heterojunction drives highly efficient catalytic cascades, disrupting redox homeostasis and inducing metabolic stress by converting O₂ to ·O₂<sup>−</sup>, H₂O₂ to ·OH, GSH to GSSG, NADH to NAD<sup>+</sup>, and lactate to pyruvate. The nanorobot directly targets mitochondria to reprogram tumor metabolism and trigger cuproptosis. Meanwhile, lactate oxidase (LOX), encapsulated within the engineered exosomes, depletes excess lactate to relieve immunosuppression and boost antitumor immunity. In CRC models, these nanorobots exhibit strong barrier penetration, precise targeting, and deep tumor infiltration, offering a multifunctional and metabolically disruptive therapeutic approach.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 3","pages":"Article 102750"},"PeriodicalIF":19.6,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194962","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}
Zeolites, traditionally defined as crystalline porous aluminosilicates, are among the most effective catalysts in chemical industry. Although, zeolites are often considered as rigid materials, emerging evidence reveals underexplored features related to the flexibility of zeolite frameworks. This dynamic property, along with structural defects, allows zeolites to process molecules larger than their nominal pore apertures under specific stimuli. This perspective examines two key aspects of zeolite flexibility: (1) inferring framework flexibility based on reactivity trends and (2) utilizing this flexibility to improve catalytic performance. Tailoring zeolite flexibility is increasingly recognized as a critical parameter for optimizing catalytic performance. Several examples highlighting the impact of zeolite flexibility on molecular diffusion, adsorption, and reaction processes are presented here. The discussion underscores the critical role of advanced characterization and molecular simulations in guiding the design and synthesis of flexible zeolite catalysts, paving the way for more efficient and sustainable catalytic processes.
{"title":"Zeolite framework flexibility: A new dimension for zeolite catalysts","authors":"Chunzheng Wang , Eddy Dib , Hailing Guo , Svetlana Mintova","doi":"10.1016/j.chempr.2025.102888","DOIUrl":"10.1016/j.chempr.2025.102888","url":null,"abstract":"<div><div>Zeolites, traditionally defined as crystalline porous aluminosilicates, are among the most effective catalysts in chemical industry. Although, zeolites are often considered as rigid materials, emerging evidence reveals underexplored features related to the flexibility of zeolite frameworks. This dynamic property, along with structural defects, allows zeolites to process molecules larger than their nominal pore apertures under specific stimuli. This perspective examines two key aspects of zeolite flexibility: (1) inferring framework flexibility based on reactivity trends and (2) utilizing this flexibility to improve catalytic performance. Tailoring zeolite flexibility is increasingly recognized as a critical parameter for optimizing catalytic performance. Several examples highlighting the impact of zeolite flexibility on molecular diffusion, adsorption, and reaction processes are presented here. The discussion underscores the critical role of advanced characterization and molecular simulations in guiding the design and synthesis of flexible zeolite catalysts, paving the way for more efficient and sustainable catalytic processes.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 3","pages":"Article 102888"},"PeriodicalIF":19.6,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146205573","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 : 2026-03-12Epub Date: 2026-02-20DOI: 10.1016/j.chempr.2025.102909
Matthew J. Evans , Cameron Jones
Redox catalysis promoted by molecular aluminum complexes has not been previously documented. Now in Nature, Zhang and Liu report the use of an aluminum(I) redox catalyst for the regioselective assembly of 1,2,4-substituted benzenes from terminal alkynes. This work provides a foundational blueprint for designing redox-active aluminum complexes for future homogeneous catalysis.
{"title":"Aluminum redox catalysis has a ring to it","authors":"Matthew J. Evans , Cameron Jones","doi":"10.1016/j.chempr.2025.102909","DOIUrl":"10.1016/j.chempr.2025.102909","url":null,"abstract":"<div><div>Redox catalysis promoted by molecular aluminum complexes has not been previously documented. Now in <em>Nature</em>, Zhang and Liu report the use of an aluminum(I) redox catalyst for the regioselective assembly of 1,2,4-substituted benzenes from terminal alkynes. This work provides a foundational blueprint for designing redox-active aluminum complexes for future homogeneous catalysis.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 3","pages":"Article 102909"},"PeriodicalIF":19.6,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147412629","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 : 2026-03-12Epub Date: 2025-10-15DOI: 10.1016/j.chempr.2025.102781
Ho-Yin Tse , Hanno C. Erythropel , Andreas Backhaus , Darren S. Lee , Shun Cheung Cheng , Chi Shun Yeung , David Lee Phillips , Julie B. Zimmerman , Paul T. Anastas
The development of sustainable solid-state emitters remains challenging because of the reliance on toxic metals, complex synthetic procedures, and non-renewable starting materials. This study demonstrates the development of solid-state emitters based on lignin, a renewable byproduct of the paper industry, and the amino acid histidine or its methyl ester through simple anti-solvent crystallization under mild conditions. The prepared materials exhibited excited-state proton transfer (ESPT)-induced fluorescence and achieved optimal performance at 0.43–0.62 mol % phenolic hydroxyl content. Notably, the lignin/histidine methyl ester emitter displayed room-temperature afterglow phosphorescence with lifetimes of up to 359 ms without requiring heavy atoms for intersystem crossing. Using powder X-ray diffraction (pXRD) and ultraviolet-visible (UV-vis) data, we postulate that the histidine methyl ester host matrix provides sufficient framework rigidity and H-aggregation to enable efficient intersystem crossing and triplet-excited-state stabilization. This work offers a sustainable strategy for tunable and renewably sourced solid-state photoluminescent materials for a variety of applications.
{"title":"Renewably sourced amino-acid- and lignin-based solid-state emitters","authors":"Ho-Yin Tse , Hanno C. Erythropel , Andreas Backhaus , Darren S. Lee , Shun Cheung Cheng , Chi Shun Yeung , David Lee Phillips , Julie B. Zimmerman , Paul T. Anastas","doi":"10.1016/j.chempr.2025.102781","DOIUrl":"10.1016/j.chempr.2025.102781","url":null,"abstract":"<div><div>The development of sustainable solid-state emitters remains challenging because of the reliance on toxic metals, complex synthetic procedures, and non-renewable starting materials. This study demonstrates the development of solid-state emitters based on lignin, a renewable byproduct of the paper industry, and the amino acid histidine or its methyl ester through simple anti-solvent crystallization under mild conditions. The prepared materials exhibited excited-state proton transfer (ESPT)-induced fluorescence and achieved optimal performance at 0.43–0.62 mol % phenolic hydroxyl content. Notably, the lignin/histidine methyl ester emitter displayed room-temperature afterglow phosphorescence with lifetimes of up to 359 ms without requiring heavy atoms for intersystem crossing. Using powder X-ray diffraction (pXRD) and ultraviolet-visible (UV-vis) data, we postulate that the histidine methyl ester host matrix provides sufficient framework rigidity and H-aggregation to enable efficient intersystem crossing and triplet-excited-state stabilization. This work offers a sustainable strategy for tunable and renewably sourced solid-state photoluminescent materials for a variety of applications.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 3","pages":"Article 102781"},"PeriodicalIF":19.6,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289329","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 : 2026-03-12Epub Date: 2026-02-25DOI: 10.1016/j.chempr.2025.102876
Callum S. Begg , Mark P. Walsh , Joseph M. Phelps , Emma H. Wolpert , Alexander D. Lee , Emanuella F. Fiandra , Emma F.G. Winful , Abby R. Haworth , Dmitry S. Yufit , Juan A. Aguilar , Toby J. Blundell , Karen E. Johnston , Clare S. Mahon , Kim E. Jelfs , Matthew O. Kitching
The selective recognition of ammonium cations fundamentally relies on their degree of substitution. In biological systems, proteins can preferentially bind more substituted ammonium cations over less substituted homologs. By contrast, the stronger hydrogen-bond donor ability and enhanced cation-π interactions of less substituted cations would predict the preferential recognition of these species. Here, we show that combining supramolecular recognition with solid-phase abstraction enables the selective abstraction of quaternary ammonium cations across diverse cation scaffolds in the solid crystalline state. Quaternary ammonium cations access a lower-energy solid state than tertiary counterparts through multipoint binding to an adaptive array of isostructural BINOL·counterion networks. The preferential abstraction of quaternary ammonium cations from mixtures of homologous cations proceeds under thermodynamic control with excellent selectivity and remains operative even under aqueous conditions.
{"title":"Selective recognition of quaternary ammonium cations","authors":"Callum S. Begg , Mark P. Walsh , Joseph M. Phelps , Emma H. Wolpert , Alexander D. Lee , Emanuella F. Fiandra , Emma F.G. Winful , Abby R. Haworth , Dmitry S. Yufit , Juan A. Aguilar , Toby J. Blundell , Karen E. Johnston , Clare S. Mahon , Kim E. Jelfs , Matthew O. Kitching","doi":"10.1016/j.chempr.2025.102876","DOIUrl":"10.1016/j.chempr.2025.102876","url":null,"abstract":"<div><div>The selective recognition of ammonium cations fundamentally relies on their degree of substitution. In biological systems, proteins can preferentially bind more substituted ammonium cations over less substituted homologs. By contrast, the stronger hydrogen-bond donor ability and enhanced cation-π interactions of less substituted cations would predict the preferential recognition of these species. Here, we show that combining supramolecular recognition with solid-phase abstraction enables the selective abstraction of quaternary ammonium cations across diverse cation scaffolds in the solid crystalline state. Quaternary ammonium cations access a lower-energy solid state than tertiary counterparts through multipoint binding to an adaptive array of isostructural BINOL·counterion networks. The preferential abstraction of quaternary ammonium cations from mixtures of homologous cations proceeds under thermodynamic control with excellent selectivity and remains operative even under aqueous conditions.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 3","pages":"Article 102876"},"PeriodicalIF":19.6,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147330077","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 : 2026-03-12Epub Date: 2025-10-10DOI: 10.1016/j.chempr.2025.102756
Mingpeng Li , Waqar Ali Memon , Zihao Deng , Huan Wang , Shilong Xiong , Heng Li , Top Archie Dela Peña , Cuifen Zhang , Yunpeng Wang , Jiaying Wu , Zaifei Ma , Nan Zheng , Leilei Tian , Feng He
Nitration is rarely employed to optimize non-fullerene acceptors (NFAs) owing to the pronounced steric hindrance and strong electron-withdrawing inductive effects of nitro groups. This study presents a site-specific nitration strategy to systematically modulate NFA properties and photovoltaic performance. A series of nitrated and non-nitrated NFAs were synthesized, exhibiting distinct energy levels, molecular configurations, and packing modes. Notably, the quasi-planar heterojunction (Q-PHJ) device based on NO2Q-2F, which incorporates a central nitration site, achieved a champion efficiency of 19.14% and an extended T80 lifetime of 6,450 h under dark storage conditions, attributed to its tighter three-dimensional network stacking. In contrast, the HQ-NO2-based device, which features terminal nitration, yielded a lower efficiency of 12.45%. This work underscores the critical role of nitration positioning in unlocking the potential of NFAs. It also provides new opportunities to further explore the impact of nitration on photovoltaic performance for developing advanced organic semiconductors.
{"title":"Photovoltaic potential of nitro-functionalized non-fullerene acceptors depends on its bonding site","authors":"Mingpeng Li , Waqar Ali Memon , Zihao Deng , Huan Wang , Shilong Xiong , Heng Li , Top Archie Dela Peña , Cuifen Zhang , Yunpeng Wang , Jiaying Wu , Zaifei Ma , Nan Zheng , Leilei Tian , Feng He","doi":"10.1016/j.chempr.2025.102756","DOIUrl":"10.1016/j.chempr.2025.102756","url":null,"abstract":"<div><div>Nitration is rarely employed to optimize non-fullerene acceptors (NFAs) owing to the pronounced steric hindrance and strong electron-withdrawing inductive effects of nitro groups. This study presents a site-specific nitration strategy to systematically modulate NFA properties and photovoltaic performance. A series of nitrated and non-nitrated NFAs were synthesized, exhibiting distinct energy levels, molecular configurations, and packing modes. Notably, the quasi-planar heterojunction (Q-PHJ) device based on NO<sub>2</sub>Q-2F, which incorporates a central nitration site, achieved a champion efficiency of 19.14% and an extended <em>T</em><sub>80</sub> lifetime of 6,450 h under dark storage conditions, attributed to its tighter three-dimensional network stacking. In contrast, the HQ-NO<sub>2</sub>-based device, which features terminal nitration, yielded a lower efficiency of 12.45%. This work underscores the critical role of nitration positioning in unlocking the potential of NFAs. It also provides new opportunities to further explore the impact of nitration on photovoltaic performance for developing advanced organic semiconductors.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 3","pages":"Article 102756"},"PeriodicalIF":19.6,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255473","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 : 2026-03-12Epub Date: 2025-10-10DOI: 10.1016/j.chempr.2025.102759
Yongseok Hong , Ding Xu , Milan Delor
Exciton-polaritons (EPs) are hybrid light-matter quasiparticles that combine exciton-mediated nonlinearities with long-range coherence, ideal for energy harvesting and nonlinear optics. Optimizing EPs is predicated on a still-elusive understanding of how disorder affects their propagation and dephasing times. Here, using cutting-edge femtosecond spatiotemporal microscopy, we image EP propagation in two-dimensional semiconductors, molecular crystals, and amorphous molecular films with systematically varied exciton-phonon coupling, exciton delocalization, and static disorder. Despite possessing similar EP dispersions, we observe dramatically different transport velocities and scattering times across systems. We establish a robust scaling law linking EP scattering to exciton transfer integral, demonstrating that polaritons based on materials with large exciton bandwidths are protected against disorder even for highly excitonic EPs. This observation cannot be deduced from the systems’ linear optical properties. Our work highlights the critical role of the matter component in dictating polariton properties and provides precise guidelines for simultaneously optimizing EP propagation and nonlinearities.
{"title":"Exciton delocalization suppresses polariton scattering","authors":"Yongseok Hong , Ding Xu , Milan Delor","doi":"10.1016/j.chempr.2025.102759","DOIUrl":"10.1016/j.chempr.2025.102759","url":null,"abstract":"<div><div>Exciton-polaritons (EPs) are hybrid light-matter quasiparticles that combine exciton-mediated nonlinearities with long-range coherence, ideal for energy harvesting and nonlinear optics. Optimizing EPs is predicated on a still-elusive understanding of how disorder affects their propagation and dephasing times. Here, using cutting-edge femtosecond spatiotemporal microscopy, we image EP propagation in two-dimensional semiconductors, molecular crystals, and amorphous molecular films with systematically varied exciton-phonon coupling, exciton delocalization, and static disorder. Despite possessing similar EP dispersions, we observe dramatically different transport velocities and scattering times across systems. We establish a robust scaling law linking EP scattering to exciton transfer integral, demonstrating that polaritons based on materials with large exciton bandwidths are protected against disorder even for highly excitonic EPs. This observation cannot be deduced from the systems’ linear optical properties. Our work highlights the critical role of the matter component in dictating polariton properties and provides precise guidelines for simultaneously optimizing EP propagation and nonlinearities.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 3","pages":"Article 102759"},"PeriodicalIF":19.6,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255471","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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