Staff directory
Laura Hernández López
Doctoral Student
FPI SO 2019
laura.hernandez(ELIMINAR)@icn2.cat
Supramolecular NanoChemistry and Materials
- ORCID: 0000-0001-6394-2538
Publications
2022
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Metal–Organic Polyhedra as Building Blocks for Porous Extended Networks
Khobotov-Bakishev A., Hernández-López L., von Baeckmann C., Albalad J., Carné-Sánchez A., Maspoch D. Advanced Science; 9 (11, 2104753) 2022. 10.1002/advs.202104753. IF: 16.806
Metal–organic polyhedra (MOPs) are a subclass of coordination cages that can adsorb and host species in solution and are permanently porous in solid-state. These characteristics, together with the recent development of their orthogonal surface chemistry and the assembly of more stable cages, have awakened the latent potential of MOPs to be used as building blocks for the synthesis of extended porous networks. This review article focuses on exploring the key developments that make the extension of MOPs possible, highlighting the most remarkable examples of MOP-based soft materials and crystalline extended frameworks. Finally, the article ventures to offer future perspectives on the exploitation of MOPs in fields that still remain ripe toward the use of such unorthodox molecular porous platforms. © 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.
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Multicomponent, Functionalized HKUST-1 Analogues Assembled via Reticulation of Prefabricated Metal-Organic Polyhedral Cavities
Khobotov-Bakishev A., Von Baeckmann C., Ortín-Rubio B., Hernández-López L., Cortés-Martínez A., Martínez-Esaín J., Gándara F., Juanhuix J., Platero-Prats A.E., Faraudo J., Carné-Sánchez A., Maspoch D. Journal of the American Chemical Society; 2022. 10.1021/jacs.2c06131.
Metal-organic frameworks (MOFs) assembled from multiple building blocks exhibit greater chemical complexity and superior functionality in practical applications. Herein, we report a new approach based on using prefabricated cavities to design isoreticular multicomponent MOFs from a known parent MOF. We demonstrate this concept with the formation of multicomponent HKUST-1 analogues, using a prefabricated cavity that comprises a cuboctahedral Rh(II) metal-organic polyhedron functionalized with 24 carboxylic acid groups. The cavities are reticulated in three dimensions via Cu(II)-paddlewheel clusters and (functionalized) 1,3,5-benzenetricarboxylate linkers to form three- and four-component HKUST-1 analogues. © 2022 The Authors. Published by American Chemical Society.
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pH-Triggered Removal of Nitrogenous Organic Micropollutants from Water by Using Metal-Organic Polyhedra
Hernández-López L., Cortés-Martínez A., Parella T., Carné-Sánchez A., Maspoch D. Chemistry - A European Journal; 28 (31, e202200357) 2022. 10.1002/chem.202200357.
Water pollution threatens human and environmental health worldwide. Thus, there is a pressing need for new approaches to water purification. Herein, we report a novel supramolecular strategy based on the use of a metal-organic polyhedron (MOP) as a capture agent to remove nitrogenous organic micropollutants from water, even at very low concentrations (ppm), based exclusively on coordination chemistry at the external surface of the MOP. Specifically, we exploit the exohedral coordination positions of RhII-MOP to coordinatively sequester pollutants bearing N-donor atoms in aqueous solution, and then harness their exposed surface carboxyl groups to control their aqueous solubility through acid/base reactions. We validated this approach for removal of benzotriazole, benzothiazole, isoquinoline, and 1-napthylamine from water. © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
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Surface chemistry of metal-organic polyhedra
Albalad J., Hernández-López L., Carné-Sánchez A., Maspoch D. Chemical Communications; 58 (15): 2443 - 2454. 2022. 10.1039/d1cc07034g. IF: 6.222
Metal-organic polyhedra (MOPs) are discrete, intrinsically-porous architectures that operate at the molecular regime and, owing to peripheral reactive sites, exhibit rich surface chemistry. Researchers have recently exploited this reactivity through post-synthetic modification (PSM) to generate specialised molecular platforms that may overcome certain limitations of extended porous materials. Indeed, the combination of modular solubility, orthogonal reactive sites, and accessible cavities yields a highly versatile molecular platform for solution to solid-state applications. In this feature article, we discuss representative examples of the PSM chemistry of MOPs, from proof-of-concept studies to practical applications, and highlight future directions for the MOP field. © The Royal Society of Chemistry.
2021
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Steric Hindrance in Metal Coordination Drives the Separation of Pyridine Regioisomers Using Rhodium(II)-Based Metal–Organic Polyhedra
Hernández-López L., Martínez-Esaín J., Carné-Sánchez A., Grancha T., Faraudo J., Maspoch D. Angewandte Chemie - International Edition; 60 (20): 11406 - 11413. 2021. 10.1002/anie.202100091. IF: 15.336
The physicochemical similarity of isomers makes their chemical separation through conventional techniques energy intensive. Herein, we report that, instead of using traditional encapsulation-driven processes, steric hindrance in metal coordination on the outer surface of RhII-based metal–organic polyhedra (Rh-MOPs) can be used to separate pyridine-based regioisomers via liquid–liquid extraction. Through molecular dynamics simulations and wet experiments, we discovered that the capacity of pyridines to coordinatively bind to Rh-MOPs is determined by the positions of the pyridine substituents relative to the pyridine nitrogen and is influenced by steric hindrance. Thus, we exploited the differential solubility of bound and non-bound pyridine regioisomers to engineer liquid–liquid self-sorting systems. As a proof of concept, we separated four different equimolecular mixtures of regioisomers, including a mixture of the industrially relevant compounds 2-chloropyridine and 3-chloropyridine, isolating highly pure compounds in all cases. © 2021 Wiley-VCH GmbH
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Synthesis of Polycarboxylate Rhodium(II) Metal–Organic Polyhedra (MOPs) and their use as Building Blocks for Highly Connected Metal–Organic Frameworks (MOFs)
Grancha T., Carné-Sánchez A., Zarekarizi F., Hernández-López L., Albalad J., Khobotov A., Guillerm V., Morsali A., Juanhuix J., Gándara F., Imaz I., Maspoch D. Angewandte Chemie - International Edition; 60 (11): 5729 - 5733. 2021. 10.1002/anie.202013839. IF: 15.336
Use of preformed metal-organic polyhedra (MOPs) as supermolecular building blocks (SBBs) for the synthesis of metal-organic frameworks (MOFs) remains underexplored due to lack of robust functionalized MOPs. Herein we report the use of polycarboxylate cuboctahedral RhII-MOPs for constructing highly-connected MOFs. Cuboctahedral MOPs were functionalized with carboxylic acid groups on their 12 vertices or 24 edges through coordinative or covalent post-synthetic routes, respectively. We then used each isolated polycarboxylate RhII-MOP as 12-c cuboctahedral or 24-c rhombicuboctahedral SBBs that, upon linkage with metallic secondary building units (SBUs), afford bimetallic highly-connected MOFs. The assembly of a pre-synthesized 12-c SBB with a 4-c paddle-wheel SBU, and a 24-c SBB with a 3-c triangular CuII SBU gave rise to bimetallic MOFs having ftw (4,12)-c or rht (3,24)-c topologies, respectively. © 2020 Wiley-VCH GmbH
2019
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Phase Transfer of Rhodium(II)-Based Metal-Organic Polyhedra Bearing Coordinatively Bound Cargo Enables Molecular Separation
Grancha T., Carné-Sánchez A., Hernández-López L., Albalad J., Imaz I., Juanhuix J., Maspoch D. Journal of the American Chemical Society; 141 (45): 18349 - 18355. 2019. 10.1021/jacs.9b10403. IF: 14.695
The transfer of nanoparticles between immiscible phases can be driven by externally triggered changes in their surface composition. Interestingly, phase transfers can enhance the processing of nanoparticles and enable their use as vehicles for transporting molecular cargo. Herein we report extension of such phase transfers to encompass porous metal-organic polyhedra (MOPs). We report that a hydroxyl-functionalized, cuboctahedral Rh(II)-based MOP can be transferred between immiscible phases by pH changes or by cation-exchange reactions. We demonstrate use of this MOP to transport coordinatively bound cargo between immiscible layers, including into solvents in which the cargo is insoluble. As proof-of-concept that our phase-transfer approach could be used in chemical separation, we employed Rh(II)-based MOPs to separate a challenging mixture of structurally similar cyclic aliphatic (tetrahydrothiophene) and aromatic (thiophene) compounds. We anticipate that transport of coordinatively bound molecules will open new avenues for molecular separation based on the relative coordination affinity that the molecules have for the Rh(II) sites of MOP. Copyright © 2019 American Chemical Society.
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Protection strategies for directionally-controlled synthesis of previously inaccessible metal-organic polyhedra (MOPs): The cases of carboxylate: The amino-functionalised Rh(ii)-MOPs
Albalad J., Carné-Sánchez A., Grancha T., Hernández-López L., Maspoch D. Chemical Communications; 55 (85): 12785 - 12788. 2019. 10.1039/c9cc07083d. IF: 6.164
Herein we report that strategic use of protecting groups in coordination reactions enables directional inhibition that leads to synthesis of highly functionalised metal-organic polyhedra (MOPs), rather than of the extended coordination networks. Using this approach, we functionalised two new porous cuboctahedral Rh(ii)-based MOPs with 24 peripheral carboxylic acid groups or 24 peripheral amino groups. This journal is © The Royal Society of Chemistry.