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Issue 26, 2014
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Copper–organic frameworks assembled from in situ generated 5-(4-pyridyl)tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols

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Abstract

Two new metal–organic compounds {[Cu33-4-ptz)42-N3)2(DMF)2](DMF)2}n (1) and {[Cu(4-ptz)2(H2O)2]}n (2) {4-ptz = 5-(4-pyridyl)tetrazolate} with 3D and 2D coordination networks, respectively, have been synthesized while studying the effect of reaction conditions on the coordination modes of 4-pytz by employing the [2 + 3] cycloaddition as a tool for generating in situ the 5-substituted tetrazole ligands from 4-pyridinecarbonitrile and NaN3 in the presence of a copper(II) salt. The obtained compounds have been structurally characterized and the topological analysis of 1 discloses a topologically unique trinodal 3,5,6-connected 3D network which, upon further simplification, results in a uninodal 8-connected underlying net with the bcu (body centred cubic) topology driven by the [Cu32-N3)2] cluster nodes and μ3-4-ptz linkers. In contrast, the 2D metal–organic network in 2 has been classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology assembled from the Cu nodes and μ2-4-ptz linkers. The catalytic investigations disclosed that 1 and 2 act as active catalyst precursors towards the microwave-assisted homogeneous oxidation of secondary alcohols (1-phenylethanol, cyclohexanol, 2-hexanol, 3-hexanol, 2-octanol and 3-octanol) with tert-butylhydroperoxide, leading to the yields of the corresponding ketones up to 86% (TOF = 430 h−1) and 58% (TOF = 290 h−1) in the oxidation of 1-phenylethanol and cyclohexanol, respectively, after 1 h under low power (10 W) microwave irradiation, and in the absence of any added solvent or additive.

Graphical abstract: Copper–organic frameworks assembled from in situ generated 5-(4-pyridyl)tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols

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Publication details

The article was received on 20 Feb 2014, accepted on 30 Apr 2014 and first published on 01 May 2014


Article type: Paper
DOI: 10.1039/C4DT00531G
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2014,43, 9944-9954
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    Copper–organic frameworks assembled from in situ generated 5-(4-pyridyl)tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols

    R. Nasani, M. Saha, S. M. Mobin, L. M. D. R. S. Martins, A. J. L. Pombeiro, A. M. Kirillov and S. Mukhopadhyay, Dalton Trans., 2014, 43, 9944
    DOI: 10.1039/C4DT00531G

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