: Reticular materials constructed from regular molecular building blocks (MBBs) have been widely explored in the past three decades. Recently, there has been increasing interest in the assembly of novel, intricate materials using less-symmetric ligands; however, current methods for predicting structure are not amenable to this increased complexity. To address this gap, we propose herein a generalised version of the net-clipping approach for anticipating the topology of metal-organic frameworks (MOFs) assembled from organic linkers and different polygonal and polyhedral MBBs. It relies on the generation of less-symmetric nets with less-connected linkers, via the rational deconstruction of more-symmetric and more-connected linkers in edge-transitive nets. We applied our top-down strategy to edge-transitive nets containing 4-c tetrahedral, 6-c hexagonal, 8-c cubic or 12-c hexagonal prism linkers, envisaging the formation of 102 derived and 46 clipped nets. Among these, we report 33 new derived nets (icn7-icn39) and 6 new clipped nets (icn1-icn6). Importantly, the feasibility of using net-clipping to anticipate clipped nets is supported by literature examples and new experimental additions. Finally, we suggest and illustrate that net-clipping can be extended to less-regular, non-edge transitive nets as well as to covalent-organic frameworks (COFs), thus opening new avenues for the rational design of new reticular materials exhibiting unprecedented topologies.

Net-clipping as a top-down approach for the prediction of topologies of MOFs built from reduced-symmetry linkers / B. Ortín-Rubio, J. Rostoll-Berenguer, C. Vila, D.M. Proserpio, V. Guillerm, J. Juanhuix, I. Imaz, D. Maspoch. - In: CHEMICAL SCIENCE. - ISSN 2041-6520. - 14:45(2023 Nov 22), pp. 12984-12994. [10.1039/d3sc04406h]

Net-clipping as a top-down approach for the prediction of topologies of MOFs built from reduced-symmetry linkers

D.M. Proserpio;
2023

Abstract

: Reticular materials constructed from regular molecular building blocks (MBBs) have been widely explored in the past three decades. Recently, there has been increasing interest in the assembly of novel, intricate materials using less-symmetric ligands; however, current methods for predicting structure are not amenable to this increased complexity. To address this gap, we propose herein a generalised version of the net-clipping approach for anticipating the topology of metal-organic frameworks (MOFs) assembled from organic linkers and different polygonal and polyhedral MBBs. It relies on the generation of less-symmetric nets with less-connected linkers, via the rational deconstruction of more-symmetric and more-connected linkers in edge-transitive nets. We applied our top-down strategy to edge-transitive nets containing 4-c tetrahedral, 6-c hexagonal, 8-c cubic or 12-c hexagonal prism linkers, envisaging the formation of 102 derived and 46 clipped nets. Among these, we report 33 new derived nets (icn7-icn39) and 6 new clipped nets (icn1-icn6). Importantly, the feasibility of using net-clipping to anticipate clipped nets is supported by literature examples and new experimental additions. Finally, we suggest and illustrate that net-clipping can be extended to less-regular, non-edge transitive nets as well as to covalent-organic frameworks (COFs), thus opening new avenues for the rational design of new reticular materials exhibiting unprecedented topologies.
Settore CHIM/03 - Chimica Generale e Inorganica
   Clip-off Chemistry: Design and Synthesis of New Materials via Programmable Disassembly of Reticular Materials
   CLIPOFF-CHEM
   European Commission
   Horizon 2020 Framework Programme
   101019003

   Nature Inspired Crystal Engineering (NICE)
   NICE
   MINISTERO DELL'ISTRUZIONE E DEL MERITO
   2020Y2CZJ2_004
22-nov-2023
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/1019410
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