Issue 34, 2020

Formation of a robust, double-walled LiMOF from an L-shaped di-substituted N-heterocyclic adamantane-based ligand

Abstract

The properties of adamantane render it an attractive building block towards the synthesis of robust frameworks. This work describes the synthesis of the L-shaped 1,3-bis(3′-carboxypyridine)adamantane (L1) ligand and the corresponding Li(I), Zn(II) and Cu(II) frameworks. Three topologically analogous Li(I) frameworks LiMOF12, LiMOF30 and LiMOF50 are reported, with calculated solvent accessible void volumes of 46, 43 and 36%, respectively. The reaction between the carboxylate groups of L1 and the Li(I) cations resulted in the formation of Li-carboxylate rods. The Li-carboxylate rods contributed to the formation of a double-walled MOF with large, open one dimensional channels. The synergistic effect of the double wall, lithium-carboxylate rods and the adamantane core itself, resulted in the formation of a robust network stable up to temperatures of 300–350 °C and a minimum of three months stability in air. Furthermore, complexation of L1 with Cu(BF4)2·H2O and Zn(CF3SO3)2 provided a 2D → 3D interpenetrated network containing a classic dimeric copper paddle-wheel SBU, and an infinite 1D chain which extended into a 3D structure facilitated by hydrogen-bonding interactions, respectively.

Graphical abstract: Formation of a robust, double-walled LiMOF from an L-shaped di-substituted N-heterocyclic adamantane-based ligand

Supplementary files

Article information

Article type
Paper
Submitted
10 Jul 2020
Accepted
11 Aug 2020
First published
12 Aug 2020

Dalton Trans., 2020,49, 12009-12017

Formation of a robust, double-walled LiMOF from an L-shaped di-substituted N-heterocyclic adamantane-based ligand

J. C. C. Houlihan, S. C. Moratti and L. R. Hanton, Dalton Trans., 2020, 49, 12009 DOI: 10.1039/D0DT02437F

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