Formation of highly interpenetrated frameworks is demonstrated. An interesting observation is the presence of very large adamantane-shaped cages in a single network, making these crystals new entries in the collection of diamondoid-type metal-organic frameworks (MOFs). The frameworks were constructed by assembling tetrahedral pyridine ligands and copper dichloride. Currently, the networks' degree of interpenetration is among the highest reported and increases when the size of the ligand is increased. Highly interpenetrated frameworks typically have low surface contact areas. In contrast, in our systems, the voids take up to 63 % of the unit cell volume. The MOFs have chiral features but are formed from achiral components. The chirality is manifested by the coordination chemistry around the metal center, the structure of the helicoidal channels, and the motifs of the individual networks. Channels of both handednesses are present within the unit cells. This phenomenon shapes the walls of the channels, which are composed of 10, 16, or 32 chains correlated with the degree of interpenetration 10-, 16-, and 32-fold, respectively. By changing the distance between the center of the ligand and the coordination moieties, we succeeded in tuning the diameter of the channels. Relatively large channels were formed, having diameters up to 31.0 angstrom x14.8 angstrom.

Chiral Motifs in Highly Interpenetrated Metal–Organic Frameworks Formed from Achiral Tetrahedral Ligands / Q. Wen, M. Chiara di Gregorio, L.J.W. Shimon, I. Pinkas, N. Malik, A. Kossoy, E.V. Alexandrov, D.M. Proserpio, M. Lahav, M.E. van der Boom. - In: CHEMISTRY. - ISSN 1521-3765. - 28:54(2022), pp. e202201108.1-e202201108.8. [10.1002/chem.202201108]

Chiral Motifs in Highly Interpenetrated Metal–Organic Frameworks Formed from Achiral Tetrahedral Ligands

D.M. Proserpio
;
2022

Abstract

Formation of highly interpenetrated frameworks is demonstrated. An interesting observation is the presence of very large adamantane-shaped cages in a single network, making these crystals new entries in the collection of diamondoid-type metal-organic frameworks (MOFs). The frameworks were constructed by assembling tetrahedral pyridine ligands and copper dichloride. Currently, the networks' degree of interpenetration is among the highest reported and increases when the size of the ligand is increased. Highly interpenetrated frameworks typically have low surface contact areas. In contrast, in our systems, the voids take up to 63 % of the unit cell volume. The MOFs have chiral features but are formed from achiral components. The chirality is manifested by the coordination chemistry around the metal center, the structure of the helicoidal channels, and the motifs of the individual networks. Channels of both handednesses are present within the unit cells. This phenomenon shapes the walls of the channels, which are composed of 10, 16, or 32 chains correlated with the degree of interpenetration 10-, 16-, and 32-fold, respectively. By changing the distance between the center of the ligand and the coordination moieties, we succeeded in tuning the diameter of the channels. Relatively large channels were formed, having diameters up to 31.0 angstrom x14.8 angstrom.
channels; diamondoid networks; interpenetration; metal-organic frameworks; symmetry breaking
Settore CHIM/03 - Chimica Generale e Inorganica
PRIN202022DPROS_01 - Nature Inspired Crystal Engineering (NICE) - PROSERPIO, DAVIDE MARIA - PRIN2020 - PRIN bando 2020 - 2022
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/939457
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