Issue 28, 2014

Utilising hinged ligands in MOF synthesis: a covalent linking strategy for forming 3D MOFs

Abstract

Here we show that connecting two equivalents of a bis-pyrazolymethane ‘hinged’ link by a carbon–carbon bond characteristically ‘extends’ the 2D layered metal–organic frameworks (MOFs) typically formed with such compounds into 3D MOF materials. 1,1,2,2-Tetrakis[4-(4-carboxyphenyl)-1H-pyrazol-1-yl]ethane (L) was prepared in three steps and upon reaction with late transition metals, namely copper(II), cadmium(II) and zinc(II), gave 3D MOFs [Cu2(L)(H2O)2] 1.4DMF and [M2LxDMF (M = Zn, x = 1; M = Cd, x = 1.75). The 3D MOFs display gating behaviour in their adsorption isotherms, consistent with 3rd generation flexible structures. Furthermore, the 3D MOFs showed appreciable affinity for CO2 at 293 K however, due to the larger pore sizes, molecular sieving of CO2/N2 was not observed. Reaction of L with cobalt(II) gave a 3D hydrogen-bonded network incorporating 1D coordination polymer chains that is topologically equivalent to the Zn and Cd MOFs. The strategy outlined here demonstrates a novel route for designing more chemically and thermally robust 3D MOFs from 2D layered materials.

Graphical abstract: Utilising hinged ligands in MOF synthesis: a covalent linking strategy for forming 3D MOFs

Supplementary files

Article information

Article type
Paper
Submitted
24 Jan 2014
Accepted
28 Feb 2014
First published
04 Mar 2014

CrystEngComm, 2014,16, 6364-6371

Author version available

Utilising hinged ligands in MOF synthesis: a covalent linking strategy for forming 3D MOFs

C. J. Coghlan, C. J. Sumby and C. J. Doonan, CrystEngComm, 2014, 16, 6364 DOI: 10.1039/C4CE00181H

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements