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Metal–organic frameworks constructed from an [MS4Cux]x−2 (M = W, Mo) unit: isomerization of the cluster unit induced by temperature†
*ab
He-Gen
Zheng
*b
and
Abstract
An [MS4Cux]x−2 cluster unit (M = W, Mo, x = 1, 2,…6) is a kind of heterothiometallic unit of versatile connectivities and geometries for building metal–organic frameworks (MOFs) of intriguing structures and properties. We here report two MOFs based on the [WS4Cux]x−2 unit and a MOF based on the [MoS4Cux]x−2 unit with 9,10-di(pyridin-4-yl)anthracene (dpa). 1 contains penta-nuclear [WS4Cu4]2+ units, which act as tetrahedral nodes and are linked by dpa ligands into a 5-fold interpenetrated diamondoid network. 2 contains an unprecedented [WS4Cu6]4+·I−·[WS4Cu6]4+ unit where two hepta-nuclear [WS4Cu6]4+ units are bridged by an I− ion, which acts as a 7-connector node, leading to a 3D network with the rare hxg-d topology. 3 is built from penta-nuclear [MoS4Cu4]2+ units and dpa ligands and is isostructural to 1. The structural difference between 1 and 2 should come from the isomerization of the [WS4Cux]x−2 unit in the synthesis processes, and we found that temperature was much more important than other factors, such as solvent, the halide anion of the CuI salt and the ratio of [NH4]2WS4 to CuI salt, for the isomerization of the [WS4Cux]x−2 unit in the formation of 1 and 2.
![Graphical abstract: Metal–organic frameworks constructed from an [MS4Cux]x−2 (M = W, Mo) unit: isomerization of the cluster unit induced by temperature](/en/Image/Get?imageInfo.ImageType=GA&imageInfo.ImageIdentifier.ManuscriptID=D1CE00647A&imageInfo.ImageIdentifier.Year=2021)
- This article is part of the themed collection: Coordination Networks
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