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Issue 3, 2012
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Zinc-1,4-benzenedicarboxylate-bipyridine frameworks – linker functionalization impacts network topology during solvothermal synthesis

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Abstract

Substitution of 1,4-benzenedicarboxylate (bdc) with additional alkoxy chains is the key to construct a family of metal–organic frameworks (MOFs) of the type [Zn2(fu-bdc)2(bipy)]n (fu-bdc = functionalized bdc; bipy = 4,4′-bipyridine) exhibiting a honeycomb-like topology instead of the default pillared square-grid topology. Both the substitution pattern of the phenyl ring of the fu-bdc linker and the chain length of the alkoxy substituents have a major impact on the structure of the derived frameworks. Substitution at positions 2 and 3 leads to the trivial pillared square-grid framework, and substitution at positions 2 and 5 or 2 and 6 yields MOFs with the honeycomb-like topology. Also, simple methoxy substituents lead to the construction of a pillared square-grid topology, whereas longer substituents like ethoxy, n-propoxy, and n-butoxy generate honeycomb-like framework structures. These honeycomb MOFs feature one-dimensional channels, which are tuneable in diameter and functionality by the choice of substituent attached to the bdc-type linker. Pure component sorption isotherms indicate that the honeycomb-like frameworks selectively adsorb CO2 over N2 and CH4.

Graphical abstract: Zinc-1,4-benzenedicarboxylate-bipyridine frameworks – linker functionalization impacts network topology during solvothermal synthesis

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Supplementary files

Article information


Submitted
26 Sep 2011
Accepted
18 Oct 2011
First published
14 Nov 2011

J. Mater. Chem., 2012,22, 909-918
Article type
Paper

Zinc-1,4-benzenedicarboxylate-bipyridine frameworks – linker functionalization impacts network topology during solvothermal synthesis

S. Henke, A. Schneemann, S. Kapoor, R. Winter and R. A. Fischer, J. Mater. Chem., 2012, 22, 909
DOI: 10.1039/C1JM14791A

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