Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102652
Guodong Li , Guoxun Ji , Shunshun Xiong , Zhen Jiang , Mengjia Yuan , Fuwan Zhai , Shujing Lin , Lixi Chen , Chunyi Yu , Mingrui Zuo , Xia Wang , Zhiyong Peng , Benxian Huang , Nannan Shen , Lanhua Chen , Yanlong Wang , Xihai Li , Xuanjun Wang , Xiaofeng Fang , Congwei Wu , Shuao Wang
The disposal of radioactive xenon and krypton generated by nuclear fission is essential for the zero emission of nuclear energy, while their efficient capture at low concentrations remains a daunting challenge. We present here a design philosophy for noble gas uptake by introducing the concept of the confinement-intensified multi-heavy-atom effect derived from the Lennard-Jones 12–6 potential, which is achieved by the construction of a previously unnoticed structural unit of a tetrahedral halogen cage arranged in a metal-organic framework (Cu(idc-I)). Record-high adsorption capacities of 128.58 and 20.83 cm3 cm−3 for Xe and Kr, respectively, were achieved at 0.1 bar and ambient temperature, along with the highest Kr Henry coefficient (10.19 mmol cm−3 bar−1). The dense tandem-arrayed tetrahedral iodine cages, as powerful binding sites have been visualized by in situ single-crystal X-ray diffraction studies and theoretical simulations, endowing Cu(idc-I) with the ability to effectively capture trace Xe and Kr from mimic nuclear reprocessing off-gas.
{"title":"Confinement-intensified multi-heavy-atom effect in a tetrahedral iodine cage enables unprecedented capture of trace xenon and krypton","authors":"Guodong Li , Guoxun Ji , Shunshun Xiong , Zhen Jiang , Mengjia Yuan , Fuwan Zhai , Shujing Lin , Lixi Chen , Chunyi Yu , Mingrui Zuo , Xia Wang , Zhiyong Peng , Benxian Huang , Nannan Shen , Lanhua Chen , Yanlong Wang , Xihai Li , Xuanjun Wang , Xiaofeng Fang , Congwei Wu , Shuao Wang","doi":"10.1016/j.chempr.2025.102652","DOIUrl":"10.1016/j.chempr.2025.102652","url":null,"abstract":"<div><div><span><span>The disposal of radioactive xenon and </span>krypton<span><span> generated by nuclear fission is essential for the zero emission of nuclear energy, while their efficient capture at low concentrations remains a daunting challenge. We present here a design philosophy for </span>noble gas uptake by introducing the concept of the confinement-intensified multi-heavy-atom effect derived from the Lennard-Jones 12–6 potential, which is achieved by the construction of a previously unnoticed structural unit of a tetrahedral halogen cage arranged in a metal-organic framework (Cu(idc-I)). Record-high adsorption capacities of 128.58 and 20.83 cm</span></span><sup>3</sup> cm<sup>−3</sup> for Xe and Kr, respectively, were achieved at 0.1 bar and ambient temperature, along with the highest Kr Henry coefficient (10.19 mmol cm<sup>−3</sup> bar<sup>−1</sup>). The dense tandem-arrayed tetrahedral iodine cages, as powerful binding sites have been visualized by <em>in situ</em><span> single-crystal X-ray diffraction studies and theoretical simulations, endowing Cu(idc-I) with the ability to effectively capture trace Xe and Kr from mimic nuclear reprocessing off-gas.</span></div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102652"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102650
Matthew J. Evans , Dat T. Nguyen , Joseph M. Parr , Jeremy Mullins , Rahul Mondal , Thayalan Rajeshkumar , Laurent Maron , Cameron Jones
The only molecular allotrope of phosphorus, white phosphorus, P4, is shown to coordinate to main-group metal centers, forming stable complexes, for the first time. Coordinatively unsaturated, Lewis acidic magnesium(II) complexes, Mg(EtNONAr) (EtNONAr; Ar = TCHP, 4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene, or Ar = DCHP, 4,5-bis(2,6-dicyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) react with P4 to form 1:1 and 2:1 Lewis adducts, Mg(EtNONTCHP)(η2-P4) and {Mg(EtNONDCHP)}2(μ-η2:η2-P4), respectively. The related arene-capped complexes of the heavier alkaline earth metals, M(EtNONTCHP)(η6-toluene) (M = Ca, Sr), also engage in coordination with P4 to give M(EtNONTCHP)(η6-toluene)(η1-P4). These alkaline earth metal-P4 complexes appear to reversibly bind P4 in aliphatic solvents and dissociate P4 upon dissolution in aromatic solvents. Reduction of P4 by magnesium(I) complex K2{Mg(tBuNONTrip)}2 (tBuNONTrip = 4,5-bis(2,4,6-triisopropylanilido)-2,7-di(tert-butyl)-9,9-dimethyl-xanthene) and a magnesium(I) synthon K2{Mg(EtNONTCHP)}2(μ-N2) provides entry to the planar, aromatic P42– dianion in K2{Mg(RNONAr)}2(μ-P4) (R = tBu, Ar = Trip; R = Et, Ar = TCHP), the hydrolysis of which releases PH3.
磷的唯一同素异形体，白磷，P4，首次被证明与主基团金属中心配位，形成稳定的配合物。配位不饱和刘易斯酸性镁（II）配合物Mg(EtNONAr) (EtNONAr；Ar = chp, 4,5-二（2,4,6-三环己基苯胺）-2,7-二乙基-9,9-二甲基-杂蒽，或Ar = DCHP, 4,5-二（2,6-二环己基苯胺）-2,7-二乙基-9,9-二甲基杂蒽)与P4反应，分别生成1:1和2:1的Lewis加成物Mg(EtNONTCHP)（η2-P4）和{Mg(EtNONDCHP)}2（μ-η2:η2-P4）。与之相关的较重碱土金属芳烃包盖配合物M(EtNONTCHP)（η - 6-甲苯）（M = Ca, Sr）也与P4配合生成M(EtNONTCHP)（η - 6-甲苯）（η - 1-P4）。这些碱土金属-P4配合物似乎在脂肪类溶剂中可逆地结合P4，并在芳香类溶剂中溶解P4。镁(I)配合物K2{Mg(tBuNONTrip)}2 （tBuNONTrip = 4,5-二（2,4,6-三异丙基苯基）-2,7-二（叔丁基）-9,9-二甲基-杂蒽）和镁(I)合成物K2{Mg(EtNONTCHP)}2（μ-N2）还原P4提供了进入K2{Mg(RNONAr)}2（μ-P4）中的平面芳香P42 - diion (R = tBu, Ar = Trip；R = Et, Ar = TCHP)，其水解释放PH3。
{"title":"Neutral P4 coordination and reduction at alkaline earth metal centers","authors":"Matthew J. Evans , Dat T. Nguyen , Joseph M. Parr , Jeremy Mullins , Rahul Mondal , Thayalan Rajeshkumar , Laurent Maron , Cameron Jones","doi":"10.1016/j.chempr.2025.102650","DOIUrl":"10.1016/j.chempr.2025.102650","url":null,"abstract":"<div><div>The only molecular allotrope of phosphorus, white phosphorus, P<sub>4</sub>, is shown to coordinate to main-group metal centers, forming stable complexes, for the first time. Coordinatively unsaturated, Lewis acidic magnesium(II) complexes, Mg(<sup>Et</sup>NON<sup>Ar</sup>) (<sup>Et</sup>NON<sup>Ar</sup>; Ar = TCHP, 4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene, or Ar = DCHP, 4,5-bis(2,6-dicyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) react with P<sub>4</sub><span> to form 1:1 and 2:1 Lewis adducts, Mg(</span><sup>Et</sup>NON<sup>TCHP</sup>)(η<sup>2</sup>-P<sub>4</sub>) and {Mg(<sup>Et</sup>NON<sup>DCHP</sup>)}<sub>2</sub>(μ-η<sup>2</sup>:η<sup>2</sup>-P<sub>4</sub><span>), respectively. The related arene-capped complexes of the heavier alkaline earth metals, M(</span><sup>Et</sup>NON<sup>TCHP</sup>)(η<sup>6</sup>-toluene) (M = Ca, Sr), also engage in coordination with P<sub>4</sub> to give M(<sup>Et</sup>NON<sup>TCHP</sup>)(η<sup>6</sup>-toluene)(η<sup>1</sup>-P<sub>4</sub>). These alkaline earth metal-P<sub>4</sub> complexes appear to reversibly bind P<sub>4</sub> in aliphatic solvents and dissociate P<sub>4</sub><span> upon dissolution in aromatic solvents. Reduction of P</span><sub>4</sub> by magnesium(I) complex K<sub>2</sub>{Mg(<sup><em>t</em>Bu</sup>NON<sup>Trip</sup>)}<sub>2</sub> (<sup><em>t</em>Bu</sup>NON<sup>Trip</sup> = 4,5-bis(2,4,6-triisopropylanilido)-2,7-di(tert-butyl)-9,9-dimethyl-xanthene) and a magnesium(I) synthon K<sub>2</sub>{Mg(<sup>Et</sup>NON<sup>TCHP</sup>)}<sub>2</sub>(<em>μ</em>-N<sub>2</sub>) provides entry to the planar, aromatic P<sub>4</sub><sup>2–</sup> dianion in K<sub>2</sub>{Mg(<sup>R</sup>NON<sup>Ar</sup>)}<sub>2</sub>(<em>μ</em>-P<sub>4</sub>) (R = tBu, Ar = Trip; R = Et, Ar = TCHP), the hydrolysis of which releases PH<sub>3</sub>.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102650"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102643
Jun-Jie Wang , Xing-Yuan Zhang , Jing-Yao Bai , Qian-Yi Liu , Jun Wen , Rong Zhu
Here, we report a dynamic mechanophore system enabled by Cu-catalyzed ring-opening condensation polymerization of propargyl cyclic carbonates, featuring a diyne backbone with mechanosensitive propargylic/benzyl C(sp3)-C(sp3) linkages and simultaneously unmasked hydroxy side chains. The weak C–C linkages generate stabilized mechanoradicals under stress, which recombine at ambient temperature. Meanwhile, the hydroxy side groups facilitate the seamless incorporation of macromolecular cross-linkers in polyurethane (PU) networks, yielding elastomers with enhanced tensile strength, toughness, and self-healing efficiency. Molecular weight-dependent mechanosensitivity suggests potential topological effects. This work provides an approach to high-performance dynamic networks with a sensitive mechanochemical response.
{"title":"Dynamic mechanoresponsive polymers enabled by ring-opening polymerization of cyclic propargyl carbonates","authors":"Jun-Jie Wang , Xing-Yuan Zhang , Jing-Yao Bai , Qian-Yi Liu , Jun Wen , Rong Zhu","doi":"10.1016/j.chempr.2025.102643","DOIUrl":"10.1016/j.chempr.2025.102643","url":null,"abstract":"<div><div>Here, we report a dynamic mechanophore system enabled by Cu-catalyzed ring-opening condensation polymerization of propargyl cyclic carbonates, featuring a diyne backbone with mechanosensitive propargylic/benzyl C(sp<sup>3</sup>)-C(sp<sup>3</sup>) linkages and simultaneously unmasked hydroxy side chains. The weak C–C linkages generate stabilized mechanoradicals under stress, which recombine at ambient temperature. Meanwhile, the hydroxy side groups facilitate the seamless incorporation of macromolecular cross-linkers in polyurethane (PU) networks, yielding elastomers with enhanced tensile strength, toughness, and self-healing efficiency. Molecular weight-dependent mechanosensitivity suggests potential topological effects. This work provides an approach to high-performance dynamic networks with a sensitive mechanochemical response.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102643"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102646
Jian-Xin Wang , Issatay Nadinov , Simil Thomas , Osama Shekhah , Xin Zhu , Tengyue He , Tengjiao He , Xiting Yuan , Shumei Wang , Hao Jiang , Osman M. Bakr , Husam N. Alshareef , Mohamed Eddaoudi , Omar F. Mohammed
In this study, we incorporate a small organic linker endowed with room-temperature phosphorescence properties into the metal-organic framework (MOF). The strong coordination and optimal proximity between the organic linker and heavy metal centers, along with the unique spatial arrangement of the linker, substantially enhance the efficiency of intersystem crossing and phosphorescence while suppressing the strong intermolecular π-π stacking typically observed in organic materials, thereby mitigating aggregation-caused quenching. This synergistic effect enables the efficient harvesting of triplet excitons and increases their radiative release by 50-fold. As a result, the MOF achieves more than a 50-fold enhancement in radioluminescence efficiency compared with the organic linker alone, along with a high X-ray imaging resolution of 20 lp/mm, surpassing most reported X-ray energy converters. These findings offer innovative design strategies for developing efficient MOF-based X-ray energy converters.
{"title":"An efficient metal-organic framework X-ray energy converter","authors":"Jian-Xin Wang , Issatay Nadinov , Simil Thomas , Osama Shekhah , Xin Zhu , Tengyue He , Tengjiao He , Xiting Yuan , Shumei Wang , Hao Jiang , Osman M. Bakr , Husam N. Alshareef , Mohamed Eddaoudi , Omar F. Mohammed","doi":"10.1016/j.chempr.2025.102646","DOIUrl":"10.1016/j.chempr.2025.102646","url":null,"abstract":"<div><div>In this study, we incorporate a small organic linker endowed with room-temperature phosphorescence properties into the metal-organic framework (MOF). The strong coordination and optimal proximity between the organic linker and heavy metal centers, along with the unique spatial arrangement of the linker, substantially enhance the efficiency of intersystem crossing and phosphorescence while suppressing the strong intermolecular π-π stacking typically observed in organic materials, thereby mitigating aggregation-caused quenching. This synergistic effect enables the efficient harvesting of triplet excitons and increases their radiative release by 50-fold. As a result, the MOF achieves more than a 50-fold enhancement in radioluminescence efficiency compared with the organic linker alone, along with a high X-ray imaging resolution of 20 lp/mm, surpassing most reported X-ray energy converters. These findings offer innovative design strategies for developing efficient MOF-based X-ray energy converters.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102646"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516259","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}
Enantioselective enzymes feature structured catalytic sites positioned within binding pockets. In contrast, widely occurring flat protein surfaces, which have been suggested to have emerged early in ancestral protein evolution as solvent-exposed β sheets, appear unlikely to catalyze asymmetric reactions because they lack the necessary scaffold for interacting with substrates in three dimensions. At the near-flat, water-accessible surface within the α-hemolysin transmembrane pore, we now demonstrate remarkable diastereoselectivity in hemithioacetal formation between a cysteine side chain and a series of aldehyde substrates. After protein surface remodeling by mutagenesis, diastereomeric ratios of up to 95:5 (kinetic control) and 98:2 (thermodynamic control) were achieved with a range of aromatic aldehydes. Molecular dynamics simulations confirmed asymmetric interactions between adducts and nearby side chains in a two-dimensional plane. Our findings indicate that flat protein surfaces can scaffold stereoselective chemistry, thereby expanding the designable protein space for catalyst engineering and providing insight into the origin of selective enzymes.
{"title":"Unexpected diastereoselective chemistry on a 2D protein surface","authors":"Zhong Hui Lim , Zonghua Bo , Emily Armstrong , Hagan Bayley , Yujia Qing","doi":"10.1016/j.chempr.2025.102717","DOIUrl":"10.1016/j.chempr.2025.102717","url":null,"abstract":"<div><div>Enantioselective enzymes feature structured catalytic sites positioned within binding pockets. In contrast, widely occurring flat protein surfaces, which have been suggested to have emerged early in ancestral protein evolution as solvent-exposed β sheets, appear unlikely to catalyze asymmetric reactions because they lack the necessary scaffold for interacting with substrates in three dimensions. At the near-flat, water-accessible surface within the α-hemolysin transmembrane pore, we now demonstrate remarkable diastereoselectivity in hemithioacetal formation between a cysteine side chain and a series of aldehyde substrates. After protein surface remodeling by mutagenesis, diastereomeric ratios of up to 95:5 (kinetic control) and 98:2 (thermodynamic control) were achieved with a range of aromatic aldehydes. Molecular dynamics simulations confirmed asymmetric interactions between adducts and nearby side chains in a two-dimensional plane. Our findings indicate that flat protein surfaces can scaffold stereoselective chemistry, thereby expanding the designable protein space for catalyst engineering and providing insight into the origin of selective enzymes.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102717"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144928638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102630
Sangam Jha , Soumili Roy , Antara Reja , Ajeet Kumar Singh , Lisa Roy , Dibyendu Das
Early compartmentalized systems built from simple building blocks had to develop complex functions to self-sustain in a fluctuating environment under non-equilibrium conditions. Herein, we report the generation of membrane-bound confinements from the self-assembly of bolaamphiphile building blocks accessed via the spontaneous imine bond formation between two simple molecules: a dipeptide and a thermodynamically activated ester. The self-assembled vesicular structures demonstrated a native hydrolase-like activity, leading to the degradation of the ester bond of the building block (negative feedback) and subsequently to an autonomous disassembly. The dynamic vesicles could further demonstrate autopoietic behavior as they could promote the regeneration of its own building block from suitable precursors (positive feedback) by exploiting its native hydrolytic ability realized through a chemical reaction network.
{"title":"Non-equilibrium autopoietic vesicles driven by intrinsic catalysis","authors":"Sangam Jha , Soumili Roy , Antara Reja , Ajeet Kumar Singh , Lisa Roy , Dibyendu Das","doi":"10.1016/j.chempr.2025.102630","DOIUrl":"10.1016/j.chempr.2025.102630","url":null,"abstract":"<div><div><span>Early compartmentalized systems built from simple building blocks had to develop complex functions to self-sustain in a fluctuating environment under non-equilibrium conditions. Herein, we report the generation of membrane-bound confinements from the self-assembly of bolaamphiphile building blocks accessed via the spontaneous </span>imine<span> bond formation between two simple molecules: a dipeptide and a thermodynamically activated ester. The self-assembled vesicular structures demonstrated a native hydrolase-like activity, leading to the degradation of the ester bond of the building block (negative feedback) and subsequently to an autonomous disassembly. The dynamic vesicles could further demonstrate autopoietic behavior as they could promote the regeneration of its own building block from suitable precursors (positive feedback) by exploiting its native hydrolytic ability realized through a chemical reaction network.</span></div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102630"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144341352","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102663
Jinqi Li , Huajie Zhu , Hanxiao Wang , Chenyang Zhao , Guanghui Ouyang , Minghua Liu
Although chiral nanostructures have been extensively studied, the fabrication of topological entities such as toroidal assemblies and their higher-order fused or catenated structures remains a formidable challenge. Here, we demonstrate a hierarchical assembly paradigm using a C3-symmetric benzene-1,3,5-tricarboxamide that enables the topological evolution of varied nanoarchitectures, such as discrete nanotoroids, fused super-nanotoroids containing up to 21 toroidal units, and nano-[2]catenanes. Our experimental and calculation results demonstrated that C3 molecules tended to form helical nanofibers with unexpected curvature due to both molecular chirality and bulky side chains. Further longitudinal extension and lateral lamellar packing of primary one-dimensional stacks led to the formation of dominant nanotoroids and stochastic nano-[2]catenanes with chiroptical signals and circularly polarized luminescence through an adaptive templating method. This work presents a cyclization-driven precise assembly of topologically discrete, fused, and catenated nanotoroids, unveiling the synergistic merging of chiral hierarchy and topological architectures in supramolecular self-assembly systems.
{"title":"Chiral C3-symmetric molecule assembly enabling topological nanotoroid, fused nanotoroid, and nanocatenane","authors":"Jinqi Li , Huajie Zhu , Hanxiao Wang , Chenyang Zhao , Guanghui Ouyang , Minghua Liu","doi":"10.1016/j.chempr.2025.102663","DOIUrl":"10.1016/j.chempr.2025.102663","url":null,"abstract":"<div><div>Although chiral nanostructures have been extensively studied, the fabrication of topological entities such as toroidal assemblies and their higher-order fused or catenated structures remains a formidable challenge. Here, we demonstrate a hierarchical assembly paradigm using a C3-symmetric benzene-1,3,5-tricarboxamide that enables the topological evolution of varied nanoarchitectures, such as discrete nanotoroids, fused super-nanotoroids containing up to 21 toroidal units, and nano-[2]catenanes. Our experimental and calculation results demonstrated that C3 molecules tended to form helical nanofibers with unexpected curvature due to both molecular chirality and bulky side chains. Further longitudinal extension and lateral lamellar packing of primary one-dimensional stacks led to the formation of dominant nanotoroids and stochastic nano-[2]catenanes with chiroptical signals and circularly polarized luminescence through an adaptive templating method. This work presents a cyclization-driven precise assembly of topologically discrete, fused, and catenated nanotoroids, unveiling the synergistic merging of chiral hierarchy and topological architectures in supramolecular self-assembly systems.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102663"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144630084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102714
Solhye Choe , Chaerin Lim , Sunghoon Kang , Eunsung Lee
The stabilization of organic radicals has long been a challenge due to their intrinsic reactivity. N-Heterocyclic carbenes (NHCs), with their unique electronic and steric properties, have emerged as powerful tools for stabilizing persistent radicals. This review highlights the latest advancements in carbene-supported organic radicals, covering key structural motifs, electronic properties, and implications for chemical reactivity. We discuss recent breakthroughs in the design of radical species derived from NHCs, cyclic (alkyl)(amino)carbenes (CAACs), and diamidocarbenes (DACs). The relationships among radical stability, spin delocalization, and functional applications are systematically discussed, particularly in the context of redox-active materials, photocatalysis, and electronic devices. This work underscores the broader significance of NHC-stabilized radicals in fundamental chemistry and applied sciences, offering insights into future directions for the field.
{"title":"N-Heterocyclic carbene-derived second-period main-group radicals: Synthesis, fundamentals, and applications","authors":"Solhye Choe , Chaerin Lim , Sunghoon Kang , Eunsung Lee","doi":"10.1016/j.chempr.2025.102714","DOIUrl":"10.1016/j.chempr.2025.102714","url":null,"abstract":"<div><div>The stabilization of organic radicals has long been a challenge due to their intrinsic reactivity. N-Heterocyclic carbenes (NHCs), with their unique electronic and steric properties, have emerged as powerful tools for stabilizing persistent radicals. This review highlights the latest advancements in carbene-supported organic radicals, covering key structural motifs, electronic properties, and implications for chemical reactivity. We discuss recent breakthroughs in the design of radical species derived from NHCs, cyclic (alkyl)(amino)carbenes (CAACs), and diamidocarbenes (DACs). The relationships among radical stability, spin delocalization, and functional applications are systematically discussed, particularly in the context of redox-active materials, photocatalysis, and electronic devices. This work underscores the broader significance of NHC-stabilized radicals in fundamental chemistry and applied sciences, offering insights into future directions for the field.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102714"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144987614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102869
Xiang Li , Xiao Shen
Four-membered rings are valuable in drug discovery, but their functionalization is challenging. In a recent issue of Nature, Koh and co-workers report a photocatalytic method for the single-atom replacement of oxygen in oxetanes. This “ring-opening-closing” relay directly yields diverse azetidines, thietanes, and cyclobutanes, enabling late-stage skeletal editing of complex molecules and streamlined synthesis of drug intermediates.
{"title":"Photocatalytic single-atom replacement enables diversification of oxetanes to azetidines, thietanes, and cyclobutanes","authors":"Xiang Li , Xiao Shen","doi":"10.1016/j.chempr.2025.102869","DOIUrl":"10.1016/j.chempr.2025.102869","url":null,"abstract":"<div><div>Four-membered rings are valuable in drug discovery, but their functionalization is challenging. In a recent issue of <em>Nature</em>, Koh and co-workers report a photocatalytic method for the single-atom replacement of oxygen in oxetanes. This “ring-opening-closing” relay directly yields diverse azetidines, thietanes, and cyclobutanes, enabling late-stage skeletal editing of complex molecules and streamlined synthesis of drug intermediates.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102869"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718946","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}
We report the design of curved anthracene systems that undergo efficient Dewar isomerization upon visible-light absorption and release heat through thermally triggered reverse isomerization, with high cyclability. These systems achieve remarkably high-energy storage capacities—up to 170 kJ/mol and 0.65 MJ/kg—comparable to the best reported molecular solar thermal (MOST) materials, while offering the added capability of harnessing the standard solar spectrum and presenting chemical robustness. Notably, these curved anthracenes can be fine-tuned to store energy in a neat liquid state, presenting a promising route toward solvent-free solar thermal energy storage devices. This report highlights the potential of fully carbon-based aromatic systems to store a large quantity of solar energy via photo-induced valence isomerization and dearomatization.
{"title":"Curved anthracenes for visible-light photon energy storage via Dewar isomerization","authors":"Subhayan Chakraborty , Writam S.R. Choudhuri , Junichi Usuba , Qianfeng Qiu , Cijil Raju , Grace G.D. Han","doi":"10.1016/j.chempr.2025.102660","DOIUrl":"10.1016/j.chempr.2025.102660","url":null,"abstract":"<div><div>We report the design of curved anthracene systems that undergo efficient Dewar isomerization upon visible-light absorption and release heat through thermally triggered reverse isomerization, with high cyclability. These systems achieve remarkably high-energy storage capacities—up to 170 kJ/mol and 0.65 MJ/kg—comparable to the best reported molecular solar thermal (MOST) materials, while offering the added capability of harnessing the standard solar spectrum and presenting chemical robustness. Notably, these curved anthracenes can be fine-tuned to store energy in a neat liquid state, presenting a promising route toward solvent-free solar thermal energy storage devices. This report highlights the potential of fully carbon-based aromatic systems to store a large quantity of solar energy via photo-induced valence isomerization and dearomatization.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102660"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144630248","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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