Metal Ion and Anion-Based “Tuning” of a Supramolecular Metallogel

A bis(pyridylurea) ligand (1) forms metallogels in methanol in the presence of up to 0.5 equiv of copper(II) chloride. The metallogel has been characterized using powder X-ray diffraction, SEM, and MAS NMR spectroscopic techniques. The addition of further copper(II) chloride gives the unusual crysta...

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Bibliographic Details
Published in:Langmuir 2009-08, Vol.25 (15), p.8451-8456
Main Authors: Piepenbrock, Marc-Oliver M, Clarke, Nigel, Steed, Jonathan W
Format: Article
Language:English
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Summary:A bis(pyridylurea) ligand (1) forms metallogels in methanol in the presence of up to 0.5 equiv of copper(II) chloride. The metallogel has been characterized using powder X-ray diffraction, SEM, and MAS NMR spectroscopic techniques. The addition of further copper(II) chloride gives the unusual crystalline 4:3 coordination polymer [Cu3(1)4Cl4]Cl2·nH2O (2). In the presence of 0.5 equiv of copper(II) nitrate, the 2:1 crystalline coordination polymer [Cu(1)2](NO3)2·H2O·MeOH (5) is isolated. Both 2 and 5 have been characterized by single-crystal X-ray diffraction. Complex 5 represents a possible model for the gelator and highlights key interactions with counteranions that suggest a means to tune gel properties using anion binding. The influence of chloride and acetate anions (as their NBu4 + salts) on the rheological properties of the copper(II) chloride metallogels of 1 are investigated. The rheology of the anion-containing mixtures shows complex behavior with the gel structure apparently evolving over time.
ISSN:0743-7463
1520-5827
DOI:10.1021/la900145n