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

Autor: Wen Q; Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot, 7610001, Israel., di Gregorio MC; Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot, 7610001, Israel., Shimon LJW; Department of Chemical Research Support, Weizmann Institute of Science, Rehovot, 7610001, Israel., Pinkas I; Department of Chemical Research Support, Weizmann Institute of Science, Rehovot, 7610001, Israel., Malik N; Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot, 7610001, Israel., Kossoy A; Department of Chemical Research Support, Weizmann Institute of Science, Rehovot, 7610001, Israel., Alexandrov EV; Samara Center for Theoretical Materials Science (SCTMS), Samara State Technical University, Samara, 443100, Russia.; Samara Branch of P. N. Lebedev Physical Institute of the Russian Academy of Sciences, Samara, 443011, Russia., Proserpio DM; Dipartimento di Chimica, Università degli Studi di Milano, 20133, Milano, Italy., Lahav M; Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot, 7610001, Israel., van der Boom ME; Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot, 7610001, Israel.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2022 Sep 27; Vol. 28 (54), pp. e202201108. Date of Electronic Publication: 2022 Aug 03.
DOI: 10.1002/chem.202201108
Abstrakt: 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 Å×14.8 Å.
(© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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