Martin E. Doleschal, Arturo Espinosa Ferao, Arseni Kostenko, Fiona J. Kiefer, Shigeyoshi Inoue
This work explores the use of plumbylene-phosphinidenes to address the challenge of isolating P=Pb bonds. Herein, we report the synthesis of three N-heterocyclic carbene phosphinidene (NHCP) substituted chlorotetrylene dimers [(IDipp)PECl]2 (E = Ge, Sn, Pb; IDipp = C([N-(2,6-iPr2C6H3)CH]2)). Substituent attachment via salt metathesis (E = Sn, Pb) enables the isolation of NHCP-silyl-substituted stannylene (IDipp)PSn(SiTms2SiTol3) as well as NHCP-silyl- and NHCP-aryl-substituted plumbylenes (IDipp)PPb(SiTms2SiTol3) and (IDipp)PPb(mTer) (mTer = 2,6-Mes2C6H3, Tms = Trimethylsilyl). Access to these structures not only expands this chemistry to the heaviest of group 14 elements but also provides a deeper understanding of the substituent effect on NHCP-tetrylene bonding. Computational studies demonstrate that both silyl- and aryl-substituted species exhibit partial multiple bond character, with the silyl-substituted species showing higher bond orders and reduced polarization. This is further supported by the short P-E bond lengths observed in their solid-state structures. Finally, the formal [2+2] cycloaddition of diphenylketene to (IDipp)PPb(mTer) provides experimental evidence for the ability of NHCP-plumbylenes to serve as synthetic equivalents of P=Pb double bonds.
{"title":"The Substituent-Effect in NHCP-Plumbylenes with a Phosphaplumbene Character","authors":"Martin E. Doleschal, Arturo Espinosa Ferao, Arseni Kostenko, Fiona J. Kiefer, Shigeyoshi Inoue","doi":"10.1002/anie.202422186","DOIUrl":"https://doi.org/10.1002/anie.202422186","url":null,"abstract":"This work explores the use of plumbylene-phosphinidenes to address the challenge of isolating P=Pb bonds. Herein, we report the synthesis of three N-heterocyclic carbene phosphinidene (NHCP) substituted chlorotetrylene dimers [(IDipp)PECl]2 (E = Ge, Sn, Pb; IDipp = C([N-(2,6-iPr2C6H3)CH]2)). Substituent attachment via salt metathesis (E = Sn, Pb) enables the isolation of NHCP-silyl-substituted stannylene (IDipp)PSn(SiTms2SiTol3) as well as NHCP-silyl- and NHCP-aryl-substituted plumbylenes (IDipp)PPb(SiTms2SiTol3) and (IDipp)PPb(mTer) (mTer = 2,6-Mes2C6H3, Tms = Trimethylsilyl). Access to these structures not only expands this chemistry to the heaviest of group 14 elements but also provides a deeper understanding of the substituent effect on NHCP-tetrylene bonding. Computational studies demonstrate that both silyl- and aryl-substituted species exhibit partial multiple bond character, with the silyl-substituted species showing higher bond orders and reduced polarization. This is further supported by the short P-E bond lengths observed in their solid-state structures. Finally, the formal [2+2] cycloaddition of diphenylketene to (IDipp)PPb(mTer) provides experimental evidence for the ability of NHCP-plumbylenes to serve as synthetic equivalents of P=Pb double bonds.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"85 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427318","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}
Electrocatalytic acetylene semi‐hydrogenation (EASH) provides a petroleum‐independent strategy for ethylene production. However, the challenges of high overpotentials and strong hydrogen evolution competition reaction over conventional electrocatalysts at industrial current densities result in substantial energy consumption, limiting the practical application of EASH technology. Herein, zinc‐doped copper catalysts are designed and prepared via a facile impregnation and electroreduction relay method. The as‐prepared Cu‐2.7Zn catalyst exhibits an ethylene partial current density of −0.29 A cm−2 with a Faradaic efficiency of 96% and a reaction potential of −0.62 V versus reversible hydrogen electrode (RHE), surpassing the previously reported electrocatalysts. The combined results of experimental tests and theoretical calculations demonstrate zinc doping significantly enhances acetylene adsorption and accelerates reaction kinetics, leading to a notable decrease in overpotential. Furthermore, the increased *H‐*H binding energy barrier and the improved ethylene desorption on Cu‐2.7Zn effectively suppress hydrogen evolution and acetylene over‐hydrogenation, contributing to the enhancement of ethylene Faradaic efficiency.
{"title":"Electrocatalytic Acetylene Semi‐Hydrogenation to Ethylene with High Energy Efficiency","authors":"Cong Dou, Yanmei Huang, Bohang Zhao, Weiwei Lei, Bin Zhang, Yifu Yu","doi":"10.1002/anie.202423381","DOIUrl":"https://doi.org/10.1002/anie.202423381","url":null,"abstract":"Electrocatalytic acetylene semi‐hydrogenation (EASH) provides a petroleum‐independent strategy for ethylene production. However, the challenges of high overpotentials and strong hydrogen evolution competition reaction over conventional electrocatalysts at industrial current densities result in substantial energy consumption, limiting the practical application of EASH technology. Herein, zinc‐doped copper catalysts are designed and prepared via a facile impregnation and electroreduction relay method. The as‐prepared Cu‐2.7Zn catalyst exhibits an ethylene partial current density of −0.29 A cm−2 with a Faradaic efficiency of 96% and a reaction potential of −0.62 V versus reversible hydrogen electrode (RHE), surpassing the previously reported electrocatalysts. The combined results of experimental tests and theoretical calculations demonstrate zinc doping significantly enhances acetylene adsorption and accelerates reaction kinetics, leading to a notable decrease in overpotential. Furthermore, the increased *H‐*H binding energy barrier and the improved ethylene desorption on Cu‐2.7Zn effectively suppress hydrogen evolution and acetylene over‐hydrogenation, contributing to the enhancement of ethylene Faradaic efficiency.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"70 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418287","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}
Yeonsoo Lim, Gyunam Park, Hojin An, Jonghwa Han, Joonhyun Bae, Ji-Hyun Kim, Yan Lee, Kyungtae Kang, Jaeyoung Sung, Sunbum Kwon
Metabolism is a complex network of chemical reactions in which transient biomolecules are continuously produced and degraded. Mimicking this dynamic process in synthetic systems poses a considerable challenge, as it requires designs that enable the exchange of energy and matter among transient molecules. In this study, we explored a chemically driven oligoesterification process operating within a highly intricate reaction network and constructed a dynamic library of transient oligoesters. Our kinetic analysis uncovered an intriguing phenomenon: oligoesters undergo parasitic exchanges, consuming one another to sustain the system's dynamics before reaching thermodynamic equilibrium. This discovery opens new opportunities for designing synthetic systems that replicate the complexity and self‐sustaining behavior of metabolic processes.
{"title":"Metabolism‐inspired chemical reaction networks for chemically driven dissipative oligoesterification","authors":"Yeonsoo Lim, Gyunam Park, Hojin An, Jonghwa Han, Joonhyun Bae, Ji-Hyun Kim, Yan Lee, Kyungtae Kang, Jaeyoung Sung, Sunbum Kwon","doi":"10.1002/anie.202425407","DOIUrl":"https://doi.org/10.1002/anie.202425407","url":null,"abstract":"Metabolism is a complex network of chemical reactions in which transient biomolecules are continuously produced and degraded. Mimicking this dynamic process in synthetic systems poses a considerable challenge, as it requires designs that enable the exchange of energy and matter among transient molecules. In this study, we explored a chemically driven oligoesterification process operating within a highly intricate reaction network and constructed a dynamic library of transient oligoesters. Our kinetic analysis uncovered an intriguing phenomenon: oligoesters undergo parasitic exchanges, consuming one another to sustain the system's dynamics before reaching thermodynamic equilibrium. This discovery opens new opportunities for designing synthetic systems that replicate the complexity and self‐sustaining behavior of metabolic processes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418330","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}
Herein, we report a new class of earth‐abundant pincer manganese catalysts that not only enable the efficient conversion of single‐component post‐consumer polyesters with a turnover number (TON) of up to 5300, but more importantly, allow the selective upcycling of polyesters from waste plastic blends (e.g., nylon, PA; polyethylene, PE; polyurethane, PU; polyvinyl chloride, PVC; cotton) or contaminants such as pigment, aluminum, or glass into highly valuable oxygenated products under mild conditions. Detailed mechanistic studies combined with DFT calculations revealed that the exceptional efficiency of this protocol is due to the use of rationally designed quinaldine‐based PNNH‐type Mn complexes with an extended π‐system and an N‐H moiety on the side arm to simultaneously enhance the stability and reactivity of the catalyst. In addition, the incorporation of dual metal‐ligand cooperation (MLC) relay catalysis more effectively facilitates the key steps of this transformation, including H2 activation and hydrogen bond‐assisted hydride transfer.
{"title":"Selective and Efficient Upcycling of Polyesters from Waste Plastic Blends Enabled by a Rationally Designed Manganese Pincer Catalyst","authors":"Yue Hu, Yanwei Gu, Yongjing Dong, Yiqing Wang, Juanfang Xu, Yingying Han, Chijian Zhang, Yinjun Xie","doi":"10.1002/anie.202502923","DOIUrl":"https://doi.org/10.1002/anie.202502923","url":null,"abstract":"Herein, we report a new class of earth‐abundant pincer manganese catalysts that not only enable the efficient conversion of single‐component post‐consumer polyesters with a turnover number (TON) of up to 5300, but more importantly, allow the selective upcycling of polyesters from waste plastic blends (e.g., nylon, PA; polyethylene, PE; polyurethane, PU; polyvinyl chloride, PVC; cotton) or contaminants such as pigment, aluminum, or glass into highly valuable oxygenated products under mild conditions. Detailed mechanistic studies combined with DFT calculations revealed that the exceptional efficiency of this protocol is due to the use of rationally designed quinaldine‐based PNNH‐type Mn complexes with an extended π‐system and an N‐H moiety on the side arm to simultaneously enhance the stability and reactivity of the catalyst. In addition, the incorporation of dual metal‐ligand cooperation (MLC) relay catalysis more effectively facilitates the key steps of this transformation, including H2 activation and hydrogen bond‐assisted hydride transfer.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"116 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418283","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}
Jeffrey Lipshultz, Dong-Hang Tan, Agniva Das, Vincent Huang, Timothy Daniel Schoch, Abubakar Lawal Mohammed
A photochemical organocatalytic method for the protodecarboxylation of unprotected amino acids is reported. Inspired by pyridoxal 5'‐phosphate‐dependent decarboxylase enzymes, the catalytic activation of amino acid substrates by 3‐hydroxyisonicotinaldehyde enables a photochemical decarboxylation event, which can be leveraged in combination with a thiol co‐catalyst. The necessary and sufficient structural features of the pyridoxal‐like framework for photoactivity are determined using ultraviolet‐visible absorption spectroscopy. A broad scope of unprotected amino acids can be decarboxylated in this system, with selectivity between multiple carboxylates realized on the possible basis of hyperconjugation. The ability to engage simple amino acids in decarboxylative functionalization at ambient conditions using a pyridoxal‐mimicking organocatalyst enables new possibilities for the translation of biogenic amino acids into medicinally valuable amines.
{"title":"Pyridoxal‐Inspired Photo‐Decarboxylase Catalysis: Photochemical Decarboxylation of Unprotected Amino Acids","authors":"Jeffrey Lipshultz, Dong-Hang Tan, Agniva Das, Vincent Huang, Timothy Daniel Schoch, Abubakar Lawal Mohammed","doi":"10.1002/anie.202424843","DOIUrl":"https://doi.org/10.1002/anie.202424843","url":null,"abstract":"A photochemical organocatalytic method for the protodecarboxylation of unprotected amino acids is reported. Inspired by pyridoxal 5'‐phosphate‐dependent decarboxylase enzymes, the catalytic activation of amino acid substrates by 3‐hydroxyisonicotinaldehyde enables a photochemical decarboxylation event, which can be leveraged in combination with a thiol co‐catalyst. The necessary and sufficient structural features of the pyridoxal‐like framework for photoactivity are determined using ultraviolet‐visible absorption spectroscopy. A broad scope of unprotected amino acids can be decarboxylated in this system, with selectivity between multiple carboxylates realized on the possible basis of hyperconjugation. The ability to engage simple amino acids in decarboxylative functionalization at ambient conditions using a pyridoxal‐mimicking organocatalyst enables new possibilities for the translation of biogenic amino acids into medicinally valuable amines.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418284","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}
Dazhong Zhong, Qiang Fang, Runxin Du, Yaxin Jin, Chen Peng, Dongfang Cheng, Tan Li, Tao Zhao, Sheng Zhang, Yao Zheng, Qiang Zhao, Yuhan Sun, Jinping Li
Selective electrocatalytic reduction of carbon dioxide (CO2RR) into ethylene (C2H4) or ethanol (C2H5OH) is a high challenge. In this study, the rational manipulating of Cu defect sites was realized for the selective formation of C2H5OH and C2H4. Low‐coordination amorphous and medium‐coordination grain‐boundary Cu defect sites with different *OH affinity were found to play a decisive role in the selective protonation of CH2CHO*. In particular, grain‐boundary‐rich Cu (denoted as Cu‐1) that weakly adsorbed *OH and CH2CHO* favored the protonation on β‐C of CH2CHO*, leading to the selective production of C2H5OH. In contrast, amorphous Cu defect sites (denoted as Cu‐3) showed strong *OH adsorption and then strong CH2CHO* adsorption, facilitating C–O breaking and C2H4 formation. In the membrane electrode assembly (MEA) configuration, a remarkably high full‐cell energy efficiency (EE) of 29.0% for C2H5OH on Cu‐1 and an impressive high full‐cell EE of 25.6% for C2H4 on Cu‐3 were observed. In addition, a C2H4 Faradaic efficiency (FE) of 63.4±1.5% was achieved on Cu‐3 at a notable current of 12.5 A with a 25 cm‐2 MEA configuration. These results provided crucial insights into the significance of defect sites in realizing the adsorption of *OH for the selective production of C2H4 or C2H5OH.
{"title":"Selective Electrochemical CO2 Reduction to Ethylene or Ethanol via Tuning *OH Adsorption","authors":"Dazhong Zhong, Qiang Fang, Runxin Du, Yaxin Jin, Chen Peng, Dongfang Cheng, Tan Li, Tao Zhao, Sheng Zhang, Yao Zheng, Qiang Zhao, Yuhan Sun, Jinping Li","doi":"10.1002/anie.202501773","DOIUrl":"https://doi.org/10.1002/anie.202501773","url":null,"abstract":"Selective electrocatalytic reduction of carbon dioxide (CO2RR) into ethylene (C2H4) or ethanol (C2H5OH) is a high challenge. In this study, the rational manipulating of Cu defect sites was realized for the selective formation of C2H5OH and C2H4. Low‐coordination amorphous and medium‐coordination grain‐boundary Cu defect sites with different *OH affinity were found to play a decisive role in the selective protonation of CH2CHO*. In particular, grain‐boundary‐rich Cu (denoted as Cu‐1) that weakly adsorbed *OH and CH2CHO* favored the protonation on β‐C of CH2CHO*, leading to the selective production of C2H5OH. In contrast, amorphous Cu defect sites (denoted as Cu‐3) showed strong *OH adsorption and then strong CH2CHO* adsorption, facilitating C–O breaking and C2H4 formation. In the membrane electrode assembly (MEA) configuration, a remarkably high full‐cell energy efficiency (EE) of 29.0% for C2H5OH on Cu‐1 and an impressive high full‐cell EE of 25.6% for C2H4 on Cu‐3 were observed. In addition, a C2H4 Faradaic efficiency (FE) of 63.4±1.5% was achieved on Cu‐3 at a notable current of 12.5 A with a 25 cm‐2 MEA configuration. These results provided crucial insights into the significance of defect sites in realizing the adsorption of *OH for the selective production of C2H4 or C2H5OH.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"21 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418300","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}
Developing stable cathodes with high capacity and rapid redox kinetics is pivotal for aqueous zinc‐organic batteries (ZOBs). A huge challenge lies in balancing the density of active sites and electronic conductivity of organic cathodes. Herein, an azo polymer from 4,5,9,10‐pyrene‐tetraone (PTAP) possessing high active components and extended conjugated structure was achieved. The extended conjugated system linked by the azo groups facilitates extensive electron delocalization and a low band gap, which endows the PTAP with enhanced electronic conductivity reaching 4.26×10⁻3 S m⁻¹. The azo groups themselves serve as active centers for two‐electron transfer, leading to a significant increase in the density of redox‐active sites and charge storage efficiency. Moreover, strong intramolecular interactions and unique solvation structure bolster the anti‐solubility of PTAP. Consequently, PTAP‐based ZOBs exhibited high reversible capacities and rate performance, delivering 442.45 mAh g⁻¹ at 0.2 A g⁻¹ and maintaining 248.61 mAh g⁻¹ even at 10 A g⁻¹. Additionally, a ZOB showed remarkable long‐term stability after cycling over 900 hours at 5 A g⁻¹. Mechanistic studies further revealed that multi‐step coupling of carbonyl and azo groups accompanied by the Zn2+/H+ dual‐ion insertion is responsible for rapid 12‐electron transfer in PTAP.
{"title":"An Azo Polymer with Abundant Active Sites and Extended Conjugation as a Stable Cathode for High‐Performance Zinc‐Organic Batteries","authors":"Shaochun Tang, Chengwei Ye, XiaoYa Zhou","doi":"10.1002/anie.202501743","DOIUrl":"https://doi.org/10.1002/anie.202501743","url":null,"abstract":"Developing stable cathodes with high capacity and rapid redox kinetics is pivotal for aqueous zinc‐organic batteries (ZOBs). A huge challenge lies in balancing the density of active sites and electronic conductivity of organic cathodes. Herein, an azo polymer from 4,5,9,10‐pyrene‐tetraone (PTAP) possessing high active components and extended conjugated structure was achieved. The extended conjugated system linked by the azo groups facilitates extensive electron delocalization and a low band gap, which endows the PTAP with enhanced electronic conductivity reaching 4.26×10⁻3 S m⁻¹. The azo groups themselves serve as active centers for two‐electron transfer, leading to a significant increase in the density of redox‐active sites and charge storage efficiency. Moreover, strong intramolecular interactions and unique solvation structure bolster the anti‐solubility of PTAP. Consequently, PTAP‐based ZOBs exhibited high reversible capacities and rate performance, delivering 442.45 mAh g⁻¹ at 0.2 A g⁻¹ and maintaining 248.61 mAh g⁻¹ even at 10 A g⁻¹. Additionally, a ZOB showed remarkable long‐term stability after cycling over 900 hours at 5 A g⁻¹. Mechanistic studies further revealed that multi‐step coupling of carbonyl and azo groups accompanied by the Zn2+/H+ dual‐ion insertion is responsible for rapid 12‐electron transfer in PTAP.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"19 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418331","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 incorporation of volatile solid additives has emerged as an effective strategy for enhancing the performance of organic solar cells (OSCs). However, the influence of the electronic structure of these additives on morphological evolution remains insufficiently understood. Herein, 1,4‐Dibromobenzene (DBB) and 1,4‐Difluoro‐2,5‐dibromobenzene (DFBB) are introduced as volatile additives into OSCs. Theoretical calculations indicate that DFBB has a higher electrostatic potential extremum and stronger σ‐holes interaction compared to DBB, enabling more robust intermolecular interactions with acceptors. The synergistic halogen interactions between DFBB and the active layer matrix balances the differences in crystallinity between the donor and acceptor during the film formation process, promotes the formation of dense molecular packing and ordered orientation, optimizes the vertical composition distribution, and promotes the formation of domain sizes close to the exciton diffusion distance. Consequently, the PM6:L8‐BO‐based device treated with DFBB achieves an efficiency of 19.2% with a fill factor (FF) of 80.8%, which is superior to the control and DBB. Further validation across various systems, including PM6:Y6, PM6:BTP‐eC9, and D18:L8‐BO, highlights similar efficiency enhancements, with the D18:L8‐BO system achieving an outstanding PCE of 19.8%. This work demonstrates that the modulation of σ‐hole interactions in volatile additives can effectively optimize multi‐scale morphology for high‐performance OSCs.
{"title":"Manipulating σ‐Hole Interactions in Halogenated Additives for High‐Performance Organic Solar Cells with 19.8% Efficiency","authors":"Wenzhao Xiong, Yongjie Cui, Ziyue Zhang, Shenbo Zhu, Zhibo Wang, Zhaohan Chai, Huawei Hu, Yiwang Chen","doi":"10.1002/anie.202500085","DOIUrl":"https://doi.org/10.1002/anie.202500085","url":null,"abstract":"The incorporation of volatile solid additives has emerged as an effective strategy for enhancing the performance of organic solar cells (OSCs). However, the influence of the electronic structure of these additives on morphological evolution remains insufficiently understood. Herein, 1,4‐Dibromobenzene (DBB) and 1,4‐Difluoro‐2,5‐dibromobenzene (DFBB) are introduced as volatile additives into OSCs. Theoretical calculations indicate that DFBB has a higher electrostatic potential extremum and stronger σ‐holes interaction compared to DBB, enabling more robust intermolecular interactions with acceptors. The synergistic halogen interactions between DFBB and the active layer matrix balances the differences in crystallinity between the donor and acceptor during the film formation process, promotes the formation of dense molecular packing and ordered orientation, optimizes the vertical composition distribution, and promotes the formation of domain sizes close to the exciton diffusion distance. Consequently, the PM6:L8‐BO‐based device treated with DFBB achieves an efficiency of 19.2% with a fill factor (FF) of 80.8%, which is superior to the control and DBB. Further validation across various systems, including PM6:Y6, PM6:BTP‐eC9, and D18:L8‐BO, highlights similar efficiency enhancements, with the D18:L8‐BO system achieving an outstanding PCE of 19.8%. This work demonstrates that the modulation of σ‐hole interactions in volatile additives can effectively optimize multi‐scale morphology for high‐performance OSCs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418286","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}
Apart from charge transport property, polymer semiconductors with patternable and healable functions are highly demanding for the fabrication of organic circuits. Herein, by leveraging the dynamic covalent disulfide bonding of thioctic acid (TA) groups, we successfully integrate photo‐patterning and thermal‐healing capabilities into a single diketopyrrolopyrrole (DPP)‐based polymer semiconductor for the first time. The results show that the thin film of DPP‐based conjugated donor‐acceptor polymer with TA groups in the side chains exhibits excellent photo‐patterning capability under 365 nm UV light irradiation, with sensitivity (S) of 210 mJ·cm‐2 and contrast (γ) of 1.2. Importantly, the patterning process has minimal impact on thin film morphology, interchain stacking, and charge transport mobility. Moreover, the patterned thin films, which were initially scratched, can be well healed after exposure to chloroform vapor and further thermal annealing, and simultaneously the charge mobility can be restored. In comparison, the scratched thin film of PDPP4T without TA groups in the side chains achieves only 82.6% recovery of scratch depth and 54.5% recovery of charge mobility under the same conditions. These results demonstrate the feasibility of constructing multifunctional polymer semiconductors by incorporating TA groups in the side chains, offering a new pathway to lithography‐compatible, self‐healing smart flexible devices.
{"title":"Photo‐Patternable and Healable Polymer Semiconductor Enabled by Dynamic Covalent Disulfide Bonding","authors":"Xiang Xue, Cheng Li, Xiaobo Yu, Kaiyuan Chenchai, Xinyue Zhang, Xisha Zhang, Guanxin Zhang, Deqing Zhang","doi":"10.1002/anie.202425172","DOIUrl":"https://doi.org/10.1002/anie.202425172","url":null,"abstract":"Apart from charge transport property, polymer semiconductors with patternable and healable functions are highly demanding for the fabrication of organic circuits. Herein, by leveraging the dynamic covalent disulfide bonding of thioctic acid (TA) groups, we successfully integrate photo‐patterning and thermal‐healing capabilities into a single diketopyrrolopyrrole (DPP)‐based polymer semiconductor for the first time. The results show that the thin film of DPP‐based conjugated donor‐acceptor polymer with TA groups in the side chains exhibits excellent photo‐patterning capability under 365 nm UV light irradiation, with sensitivity (S) of 210 mJ·cm‐2 and contrast (γ) of 1.2. Importantly, the patterning process has minimal impact on thin film morphology, interchain stacking, and charge transport mobility. Moreover, the patterned thin films, which were initially scratched, can be well healed after exposure to chloroform vapor and further thermal annealing, and simultaneously the charge mobility can be restored. In comparison, the scratched thin film of PDPP4T without TA groups in the side chains achieves only 82.6% recovery of scratch depth and 54.5% recovery of charge mobility under the same conditions. These results demonstrate the feasibility of constructing multifunctional polymer semiconductors by incorporating TA groups in the side chains, offering a new pathway to lithography‐compatible, self‐healing smart flexible devices.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418301","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}
Jacques Lalevee, Tong Gao, Zheng Liu, Jiansong Yin, Ji Feng, Céline Dietlin, Fabrice Morlet-Savary, Michael Schmitt, Tatiana Petithory, Laurent Pieuchot, Jing Zhang, Frédéric Dumur, Pu Xiao
The development of photoinitiators (PIs) combining high initiation ability, low‐toxicity, and availability for high‐precision 3D printing is a key challenge in photopolymerization that has never been reported before. In this study, carbazole chalcone glyoxylate oxime ester derivatives (denoted as Cs, C1‐C5) containing both glyoxylate and oxime ester moieties with good light absorption properties in the visible range have been designed as type I PIs. Subsequent experimental results clearly show that the photoinitiation ability of C5 outperforms that of the benchmark commercial PIs (methyl benzoylformate (MBF) and diphenyl (2,4,6‐trimethylbenzoyl) phosphine oxide (TPO)) under the same conditions. In addition, C5 is successfully applied to 3D printing for the manufacture of large‐scale and high‐resolution object. The photochemical mechanism of C5 is systematically and comprehensively analyzed using a combination of steady state photolysis, decarboxylation reaction, fluorescence experiments, and electron spin resonance‐spin trapping (ESR‐ST) technology. Furthermore, the low‐toxicity of C5 is evidenced by cytotoxicity assays. The comprehensive molecular modeling and experimental approach adopted in this research has led to the development of novel PIs that are highly efficient and low‐toxic, and can be used for high‐precision 3D printing, which offers broad application prospects in the fields of environmental sustainability, visible light curing, and biomedical science.
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