Dispersing the catalytically more active noble metal at the single-site scale ensures maximum atom efficiency for selective heterogeneous hydrogenation over bimetallic particles. However, the low density and random location of the noble-metal atoms compromise the intrinsic activity and/or selectivity because of the resulting altered electronic structure. Here, we report that densely populating and precisely arranging Pt atoms in the form of a Pt-Fe-Pt heterotrimer not only catalyzes preferential hydrogenation of the C=O bond in crotonaldehyde (CAL) but also increases the reaction rate by 35-fold, circumventing the activity-selectivity trade-off. The Pt-Fe-Pt active site is fabricated by H2 reduction at 673 K of a Pt-Fe2O3 particle pair, wherein a 3.3 nm Pt particle sits on a 9.8 nm Fe2O3 particle. It interacts with the CAL molecule in a site-bond recognition manner: the left-end Pt atom anchors the C=C bond, whereas the central Fe atom activates the C=O bond, which is further hydrogenated by H atoms adsorbed on the right-end Pt atom.
{"title":"Fine-tuned coordination environment of Pt-Fe-Pt active site for selective heterogeneous hydrogenation of crotonaldehyde","authors":"Di Zhou, Junjun Wang, Minzhen Jian, Yong Li, Zheng Jiang, Shuang Liu, Yan Zhou, Jiake Wei, Christof Wöll, Wei-Xue Li, Yuemin Wang, Wenjie Shen","doi":"10.1016/j.chempr.2024.11.018","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.018","url":null,"abstract":"Dispersing the catalytically more active noble metal at the single-site scale ensures maximum atom efficiency for selective heterogeneous hydrogenation over bimetallic particles. However, the low density and random location of the noble-metal atoms compromise the intrinsic activity and/or selectivity because of the resulting altered electronic structure. Here, we report that densely populating and precisely arranging Pt atoms in the form of a Pt-Fe-Pt heterotrimer not only catalyzes preferential hydrogenation of the C=O bond in crotonaldehyde (CAL) but also increases the reaction rate by 35-fold, circumventing the activity-selectivity trade-off. The Pt-Fe-Pt active site is fabricated by H<sub>2</sub> reduction at 673 K of a Pt-Fe<sub>2</sub>O<sub>3</sub> particle pair, wherein a 3.3 nm Pt particle sits on a 9.8 nm Fe<sub>2</sub>O<sub>3</sub> particle. It interacts with the CAL molecule in a site-bond recognition manner: the left-end Pt atom anchors the C=C bond, whereas the central Fe atom activates the C=O bond, which is further hydrogenated by H atoms adsorbed on the right-end Pt atom.","PeriodicalId":268,"journal":{"name":"Chem","volume":"75 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917848","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 : 2025-01-03DOI: 10.1016/j.chempr.2024.11.020
Xu Chen, Dhruv Menon, Xiaoliang Wang, Meng He, Mohammad Reza Alizadeh Kiapi, Mehrdad Asgari, Yuexi Lyu, Xianhui Tang, Luke L. Keenan, William Shepard, Lik H. Wee, Sihai Yang, Omar K. Farha, David Fairen-Jimenez
Selective CO2 capture from industry is crucial for reducing emissions from fossil fuel combustion. Flexible metal-organic frameworks (MOFs) have shown promise for CO2 adsorption via differential binding and size-exclusion mechanisms. However, achieving precise pore-size control to selectively capture CO2, particularly in the presence of N2 and water, remains a challenge. Here, we demonstrate a strategy for frustrating framework flexibility in a MOF to create an optimal, confined pore environment that enhances selective CO2 recognition while maintaining high working capacity. We designed a flexible MOF, Cambridge University (CU)-4, by using a bulky cubane-derived ligand and In3+ ions that undergo dynamic breathing with a 2 Å contraction upon solvent exchange and removal. In situ synchrotron X-ray diffraction and molecular simulations reveal that the stable narrow-pore configuration creates a hydrogen-rich cavity that selectively binds CO2 via multiple hydrogen bonds. This physisorption-based CO2 recognition remains effective even at 80% humidity, making CU-4 promising for post-combustion carbon capture.
{"title":"Flexibility-frustrated porosity for enhanced selective CO2 adsorption in an ultramicroporous metal-organic framework","authors":"Xu Chen, Dhruv Menon, Xiaoliang Wang, Meng He, Mohammad Reza Alizadeh Kiapi, Mehrdad Asgari, Yuexi Lyu, Xianhui Tang, Luke L. Keenan, William Shepard, Lik H. Wee, Sihai Yang, Omar K. Farha, David Fairen-Jimenez","doi":"10.1016/j.chempr.2024.11.020","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.020","url":null,"abstract":"Selective CO<sub>2</sub> capture from industry is crucial for reducing emissions from fossil fuel combustion. Flexible metal-organic frameworks (MOFs) have shown promise for CO<sub>2</sub> adsorption via differential binding and size-exclusion mechanisms. However, achieving precise pore-size control to selectively capture CO<sub>2</sub>, particularly in the presence of N<sub>2</sub> and water, remains a challenge. Here, we demonstrate a strategy for frustrating framework flexibility in a MOF to create an optimal, confined pore environment that enhances selective CO<sub>2</sub> recognition while maintaining high working capacity. We designed a flexible MOF, Cambridge University (CU)-4, by using a bulky cubane-derived ligand and In<sup>3+</sup> ions that undergo dynamic breathing with a 2 Å contraction upon solvent exchange and removal. <em>In situ</em> synchrotron X-ray diffraction and molecular simulations reveal that the stable narrow-pore configuration creates a hydrogen-rich cavity that selectively binds CO<sub>2</sub> via multiple hydrogen bonds. This physisorption-based CO<sub>2</sub> recognition remains effective even at 80% humidity, making CU-4 promising for post-combustion carbon capture.","PeriodicalId":268,"journal":{"name":"Chem","volume":"28 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917932","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 : 2025-01-02DOI: 10.1016/j.chempr.2024.102397
Pall Thordarson, Dong Jun Kim
In this issue of Chem, Zhao et al. present a supramolecular strategy for controlling symmetry-breaking charge separation (SB-CS) through guest-mediated superexchange pathways. In a cyclophane host, guest molecules accelerate or suppress SB-CS by enhancing electron-transfer efficiency. This dynamic system enables tunable charge separation and demonstrates potential for photocatalysis, light energy conversion, and applications in organic photovoltaics.
{"title":"Supramolecular boosted superexchange","authors":"Pall Thordarson, Dong Jun Kim","doi":"10.1016/j.chempr.2024.102397","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102397","url":null,"abstract":"In this issue of <em>Chem</em>, Zhao et al. present a supramolecular strategy for controlling symmetry-breaking charge separation (SB-CS) through guest-mediated superexchange pathways. In a cyclophane host, guest molecules accelerate or suppress SB-CS by enhancing electron-transfer efficiency. This dynamic system enables tunable charge separation and demonstrates potential for photocatalysis, light energy conversion, and applications in organic photovoltaics.","PeriodicalId":268,"journal":{"name":"Chem","volume":"67 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912056","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 : 2025-01-02DOI: 10.1016/j.chempr.2024.11.014
Johannes Hahmann, Boris N. Schüpp, Aman Ishaqat, Arjuna Selvakumar, Robert Göstl, Frauke Gräter, Andreas Herrmann
Nucleic acids, such as DNA, are integral components of biological systems in that they steer many cellular processes and biotechnological applications. In addition, their monomer-precise sequence and accurately predictable structure render them an excellent model for exploring fundamental problems in nanotechnology and polymer science. In the field of polymer mechanochemistry, predetermined breaking points, called mechanophores, are used to endow macromolecules with chain-scission selectivity when subjected to external forces. However, this approach entails cumbersome chemical synthesis and limited outcome analysis. Here, we show the mechanophore-free, near-nucleotide-precise scission of nicked double-stranded DNA in a combined experimental and computational approach. We leverage next-generation sequencing to achieve monomer-level precision in assessing chain scission. Additionally, we monitor and control the scission distribution on the polymer’s backbone. Our research highlights the potential of DNA as a model polymer in the field of polymer mechanochemistry.
{"title":"Sequence-specific, mechanophore-free mechanochemistry of DNA","authors":"Johannes Hahmann, Boris N. Schüpp, Aman Ishaqat, Arjuna Selvakumar, Robert Göstl, Frauke Gräter, Andreas Herrmann","doi":"10.1016/j.chempr.2024.11.014","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.014","url":null,"abstract":"Nucleic acids, such as DNA, are integral components of biological systems in that they steer many cellular processes and biotechnological applications. In addition, their monomer-precise sequence and accurately predictable structure render them an excellent model for exploring fundamental problems in nanotechnology and polymer science. In the field of polymer mechanochemistry, predetermined breaking points, called mechanophores, are used to endow macromolecules with chain-scission selectivity when subjected to external forces. However, this approach entails cumbersome chemical synthesis and limited outcome analysis. Here, we show the mechanophore-free, near-nucleotide-precise scission of nicked double-stranded DNA in a combined experimental and computational approach. We leverage next-generation sequencing to achieve monomer-level precision in assessing chain scission. Additionally, we monitor and control the scission distribution on the polymer’s backbone. Our research highlights the potential of DNA as a model polymer in the field of polymer mechanochemistry.","PeriodicalId":268,"journal":{"name":"Chem","volume":"4 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912261","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 activation of organic halides by transition metals is one of the most important elementary processes in organic synthesis, which can be achieved by a two-electron oxidation addition process or a one-electron radical process. Currently, the ruthenium-catalyzed meta-C(sp2)–H alkylation with alkyl halides has emerged as a robust tool for remote C(sp2)–H functionalization and was unambiguously proved to occur via a radical pathway. By contrast, the modus operandi of ruthenium-catalyzed ortho-C(sp2)–H alkylation is still somewhat unclear and was proposed to occur through a two-electron manifold of ruthenium(II/IV) regime. In this context, we reported on a photo-induced ruthenium-catalyzed ortho-C(sp2)−H alkylation with secondary/primary alkyl bromides. Mechanistic studies by experiment and computation provide strong support for a ruthenium(II/III/IV) regime, involving a SET between alkyl bromide and the in situ-generated bicycloruthenated complex.
{"title":"Ruthenaphoto-catalyzed ortho-C−H alkylation with secondary alkyl halides: SET-enabled ruthenium(II/III/IV) manifold","authors":"Yulei Wang, Binbin Yuan, Xuexue Chang, Lutz Ackermann","doi":"10.1016/j.chempr.2024.12.005","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.12.005","url":null,"abstract":"The activation of organic halides by transition metals is one of the most important elementary processes in organic synthesis, which can be achieved by a two-electron oxidation addition process or a one-electron radical process. Currently, the ruthenium-catalyzed <em>meta</em>-C(sp<sup>2</sup>)–H alkylation with alkyl halides has emerged as a robust tool for remote C(sp<sup>2</sup>)–H functionalization and was unambiguously proved to occur via a radical pathway. By contrast, the modus operandi of ruthenium-catalyzed <em>ortho</em>-C(sp<sup>2</sup>)–H alkylation is still somewhat unclear and was proposed to occur through a two-electron manifold of ruthenium(II/IV) regime. In this context, we reported on a photo-induced ruthenium-catalyzed <em>ortho</em>-C(sp<sup>2</sup>)−H alkylation with secondary/primary alkyl bromides. Mechanistic studies by experiment and computation provide strong support for a ruthenium(II/III/IV) regime, involving a SET between alkyl bromide and the <em>in situ</em>-generated bicycloruthenated complex.","PeriodicalId":268,"journal":{"name":"Chem","volume":"93 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905638","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 : 2024-12-27DOI: 10.1016/j.chempr.2024.11.013
Iago Neira, Chiara Taticchi, Federico Nicoli, Massimiliano Curcio, Marcos D. Garcia, Carlos Peinador, Serena Silvi, Massimo Baroncini, Alberto Credi
The ability to exploit an energy source to drive chemical reactions away from thermodynamic equilibrium is an essential feature of life and a grand challenge for the design of fuel-driven dynamic artificial nanosystems. Here, we investigate the effect of light irradiation on the formation of supramolecular complexes composed of azobenzene-type guests and a cyclodextrin (CD) host in water. Whereas previous studies on these complexes have focused on equilibrium properties, our work explores far-from-equilibrium distributions obtained by light-driven association. We demonstrate that the relative abundance of the two CD orientational diastereomeric complexes can be inverted upon photoirradiation and showcase a ratcheted approach, employing biocompatible macrocycles and harnessing visible light, to the spontaneous formation of high-energy CD complexes with broad applicability in aqueous environments. We foresee opportunities for the development of active materials, the design of artificial metabolic networks, and the engineering of molecular machines operating under physiological conditions.
{"title":"Light-driven ratcheted formation of diastereomeric host-guest systems","authors":"Iago Neira, Chiara Taticchi, Federico Nicoli, Massimiliano Curcio, Marcos D. Garcia, Carlos Peinador, Serena Silvi, Massimo Baroncini, Alberto Credi","doi":"10.1016/j.chempr.2024.11.013","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.013","url":null,"abstract":"The ability to exploit an energy source to drive chemical reactions away from thermodynamic equilibrium is an essential feature of life and a grand challenge for the design of fuel-driven dynamic artificial nanosystems. Here, we investigate the effect of light irradiation on the formation of supramolecular complexes composed of azobenzene-type guests and a cyclodextrin (CD) host in water. Whereas previous studies on these complexes have focused on equilibrium properties, our work explores far-from-equilibrium distributions obtained by light-driven association. We demonstrate that the relative abundance of the two CD orientational diastereomeric complexes can be inverted upon photoirradiation and showcase a ratcheted approach, employing biocompatible macrocycles and harnessing visible light, to the spontaneous formation of high-energy CD complexes with broad applicability in aqueous environments. We foresee opportunities for the development of active materials, the design of artificial metabolic networks, and the engineering of molecular machines operating under physiological conditions.","PeriodicalId":268,"journal":{"name":"Chem","volume":"202 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142887867","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 : 2024-12-27DOI: 10.1016/j.chempr.2024.11.012
Marcel J. Eleveld, Juntian Wu, Kai Liu, Jim Ottelé, Omer Markovitch, Armin Kiani, Lukas C. Herold, Alessia Lasorsa, Patrick C.A. van der Wel, Sijbren Otto
Darwinian evolution of self-replicating entities most likely played a key role in the emergence of life from inanimate matter. For evolution to occur, self-replicators must (1) have structural space accessible to them, (2) occupy only part of it at any time, and (3) navigate it through mutation and selection. We describe a system of self-replicating hexameric macrocycles formed upon the mixing of two building blocks and occupying a subset of possible sequences. Specific interactions, most likely through steric zipper formation, favor a hexamer sequence where the two blocks alternate. Under different replication-destruction regimes, distinct replicator mutants are selected. With non-selective destruction (via outflow), the fastest replicators dominate. With chemically mediated, selective destruction, a mutant that balances replication speed and resistance to reduction by steric zipper formation becomes dominant. This system demonstrates a rudimentary form of Darwinian evolution, where replicators adapt to changing selection pressures through mutation and selection.
{"title":"Departure from randomness: Evolution of self-replicators that can self-sort through steric zipper formation","authors":"Marcel J. Eleveld, Juntian Wu, Kai Liu, Jim Ottelé, Omer Markovitch, Armin Kiani, Lukas C. Herold, Alessia Lasorsa, Patrick C.A. van der Wel, Sijbren Otto","doi":"10.1016/j.chempr.2024.11.012","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.012","url":null,"abstract":"Darwinian evolution of self-replicating entities most likely played a key role in the emergence of life from inanimate matter. For evolution to occur, self-replicators must (1) have structural space accessible to them, (2) occupy only part of it at any time, and (3) navigate it through mutation and selection. We describe a system of self-replicating hexameric macrocycles formed upon the mixing of two building blocks and occupying a subset of possible sequences. Specific interactions, most likely through steric zipper formation, favor a hexamer sequence where the two blocks alternate. Under different replication-destruction regimes, distinct replicator mutants are selected. With non-selective destruction (via outflow), the fastest replicators dominate. With chemically mediated, selective destruction, a mutant that balances replication speed and resistance to reduction by steric zipper formation becomes dominant. This system demonstrates a rudimentary form of Darwinian evolution, where replicators adapt to changing selection pressures through mutation and selection.","PeriodicalId":268,"journal":{"name":"Chem","volume":"58 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142887831","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 : 2024-12-23DOI: 10.1016/j.chempr.2024.11.006
Elizabeth D. Heafner, Andrew L. Smith, Cristina V. Craescu, Kenneth N. Raymond, Robert G. Bergman, F. Dean Toste
Enzyme-like enantiopure supramolecular hosts leverage non-covalent and electrostatic interactions to engage substrates in a chiral environment without direct coordination. Elucidating the mechanistic underpinnings of enantioinduction in these systems is critical to the success of this nascent field. We report herein an enantiopure Ga4L612− host-catalyzed asymmetric reduction of aromatic, heteroaromatic, and aliphatic oximes to hydroxylamines, without N–O bond cleavage, using pyridine borane as a reductant cofactor. The reaction scope and mechanistic study, in combination with data science analysis, showcase that guest recognition and enantioinduction are highly sensitive to both steric and electronic effects. Optimization of interactions between the host, oxime, and reductant within the host cavity enabled highly enantioselective reactivity (>99% ee) for even previously unreported pyridine oximes. The emergent principles outlined herein lay the foundation for future applications of these promising catalytic scaffolds toward challenging synthetic targets.
{"title":"Probing enantioinduction in confined chiral spaces through asymmetric oxime reductions","authors":"Elizabeth D. Heafner, Andrew L. Smith, Cristina V. Craescu, Kenneth N. Raymond, Robert G. Bergman, F. Dean Toste","doi":"10.1016/j.chempr.2024.11.006","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.006","url":null,"abstract":"Enzyme-like enantiopure supramolecular hosts leverage non-covalent and electrostatic interactions to engage substrates in a chiral environment without direct coordination. Elucidating the mechanistic underpinnings of enantioinduction in these systems is critical to the success of this nascent field. We report herein an enantiopure Ga<sub>4</sub>L<sub>6</sub><sup>12</sup><sup>−</sup> host-catalyzed asymmetric reduction of aromatic, heteroaromatic, and aliphatic oximes to hydroxylamines, without N–O bond cleavage, using pyridine borane as a reductant cofactor. The reaction scope and mechanistic study, in combination with data science analysis, showcase that guest recognition and enantioinduction are highly sensitive to both steric and electronic effects. Optimization of interactions between the host, oxime, and reductant within the host cavity enabled highly enantioselective reactivity (>99% ee) for even previously unreported pyridine oximes. The emergent principles outlined herein lay the foundation for future applications of these promising catalytic scaffolds toward challenging synthetic targets.","PeriodicalId":268,"journal":{"name":"Chem","volume":"113 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880050","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 : 2024-12-23DOI: 10.1016/j.chempr.2024.11.010
Brigitte A.K. Kriebisch, Christine M.E. Kriebisch
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Brigitte and Christine Kriebisch completed their MSc in chemistry at the Technical University of Munich before joining Prof. Job Boekhoven for their doctoral studies. Their fascination with biological nanomachinery that harvests chemical energy to achieve directional motion and directional pumping drives them to develop synthetic analogs that hold future potential in medical applications. For example, they can imagine nanorobots that swim through blood vessels for cargo transport or to detect tumor cells.
{"title":"Stay creative","authors":"Brigitte A.K. Kriebisch, Christine M.E. Kriebisch","doi":"10.1016/j.chempr.2024.11.010","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.010","url":null,"abstract":"<span><figure><span><img alt=\"\" height=\"331\" src=\"https://ars.els-cdn.com/content/image/1-s2.0-S2451929424005941-fx1.jpg\"/><ol><li><span><span>Download: <span>Download high-res image (331KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span><span><figure><span><img alt=\"\" height=\"331\" src=\"https://ars.els-cdn.com/content/image/1-s2.0-S2451929424005941-fx2.jpg\"/><ol><li><span><span>Download: <span>Download high-res image (322KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span>Brigitte and Christine Kriebisch completed their MSc in chemistry at the Technical University of Munich before joining Prof. Job Boekhoven for their doctoral studies. Their fascination with biological nanomachinery that harvests chemical energy to achieve directional motion and directional pumping drives them to develop synthetic analogs that hold future potential in medical applications. For example, they can imagine nanorobots that swim through blood vessels for cargo transport or to detect tumor cells.","PeriodicalId":268,"journal":{"name":"Chem","volume":"2 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880049","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}
Constructing artificial sophisticated architectures from simple small-molecular subunits by cooperative interactions remains one of the most formidable challenges. Herein, we report a complex supramolecular structure, {{[CoL(SCN)]20}{[CoL(SCN)]24}3(SO4)23(HSO4)46}·246(CH3CN) (1), that arises from the assembly of [CoL(SCN)]+ with SO42− and HSO4− (L = tris(2-benzimidazolylmethyl)amine) under solvothermal condition. The crystallization of compound 1 is driven by the cooperation of the π-π stacking interactions between [CoL(SCN)]+ cations and the hydrogen bonds between [CoL(SCN)]+ and SO42− and HSO4−. [CoL(SCN)]+ cations self-associate through intermolecular π-π stacking interactions to create two π-stacked polyhedral 512-{[CoL(SCN)]20} dodecahedra and 51262-{[CoL(SCN)]24} tetrakaidekahedra. These two π-stacked polyhedral subunits coexist in the same lattice in a 1:3 ratio and coordinate with SO42− and HSO4−, resulting in a complex Frank-Kasper (FK) A15 structure. This research demonstrates that small-molecular scaffolds can assemble into sophisticated architectures and creates exciting perspectives for constructing sophisticated clathrate structures from simple small molecules.
{"title":"Anion-coordination- and π-π-stacking-interaction-driven assembly of a complex Frank-Kasper structure","authors":"Zhu Zhuo, Zi-Ang Nan, Wen-Zheng Fu, Wei Wang, Guo-Ling Li, Ming-Yan Wu, Maochun Hong, You-Gui Huang","doi":"10.1016/j.chempr.2024.11.009","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.009","url":null,"abstract":"Constructing artificial sophisticated architectures from simple small-molecular subunits by cooperative interactions remains one of the most formidable challenges. Herein, we report a complex supramolecular structure, {{[CoL(SCN)]<sub>20</sub>}{[CoL(SCN)]<sub>24</sub>}<sub>3</sub>(SO<sub>4</sub>)<sub>23</sub>(HSO<sub>4</sub>)<sub>46</sub>}·246(CH<sub>3</sub>CN) (<strong>1</strong>), that arises from the assembly of [CoL(SCN)]<sup>+</sup> with SO<sub>4</sub><sup>2−</sup> and HSO<sub>4</sub><sup>−</sup> (L = tris(2-benzimidazolylmethyl)amine) under solvothermal condition. The crystallization of compound <strong>1</strong> is driven by the cooperation of the <em>π-π</em> stacking interactions between [CoL(SCN)]<sup>+</sup> cations and the hydrogen bonds between [CoL(SCN)]<sup>+</sup> and SO<sub>4</sub><sup>2−</sup> and HSO<sub>4</sub><sup>−</sup>. [CoL(SCN)]<sup>+</sup> cations self-associate through intermolecular <em>π-π</em> stacking interactions to create two <em>π</em>-stacked polyhedral 5<sup>12</sup>-{[CoL(SCN)]<sub>20</sub>} dodecahedra and 5<sup>12</sup>6<sup>2</sup>-{[CoL(SCN)]<sub>24</sub>} tetrakaidekahedra. These two <em>π</em>-stacked polyhedral subunits coexist in the same lattice in a 1:3 ratio and coordinate with SO<sub>4</sub><sup>2−</sup> and HSO<sub>4</sub><sup>−</sup>, resulting in a complex Frank-Kasper (FK) A15 structure. This research demonstrates that small-molecular scaffolds can assemble into sophisticated architectures and creates exciting perspectives for constructing sophisticated clathrate structures from simple small molecules.","PeriodicalId":268,"journal":{"name":"Chem","volume":"30 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832715","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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