Zheng, Q., Vilà-Nadal, L. , Lang, Z., Chen, J.-j., Long, D.-L. , Mathieson, J. S., Poblet, J. M. and Cronin, L. (2018) Self-sorting of heteroanions in the assembly of cross-shaped polyoxometalate clusters. Journal of the American Chemical Society, 140(7), pp. 2595-2601. (doi: 10.1021/jacs.7b11982) (PMID:29359931) (PMCID:PMC6075695)
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Abstract
Heteroanion (HA) moieties have a key role in templating of heteropolyoxometalate (HPA) architectures, but clusters templated by two different templates are rarely reported. Herein, we show how a cross-shaped HPA-based architecture can self-sort the HA templates by pairing two different guests into a divacant {XYW15O54} building block, with four of these building block units being linked together to complete the cross-shaped architecture. We exploited this observation to incorporate HA templates into well-defined positions within the clusters, leading to the isolation of a collection of mixed-HA templated cross-shaped polyanions [(XYW15O54)4(WO2)4]32–/36– (X = H–P, Y = Se, Te, As). The template positions have been unambiguously determined by single crystal X-ray diffraction, NMR spectroscopy, and high-resolution electrospray ionization mass spectrometry; these studies demonstrated that the mixed template containing HPA clusters are the preferred products which crystallize from the solution. Theoretical studies using DFT calculations suggest that the selective self-sorting originates from the coordination of the template in solution. The cross-shaped polyoxometalate clusters are redox-active, and the ability of molecules to accept electrons is slightly modulated by the HA incorporated as shown by differential pulse voltammetry experiments. These results indicate that the cross-shaped HPAs can be used to select templates from solution, and themselves have interesting geometries, which will be useful in developing functional molecular architectures based upon HPAs with well-defined structures and electronic properties.
Item Type: | Articles |
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Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Zheng, Ms Qi and Vila-Nadal, Dr Laia and Chen, Dr Jiajia and Mathieson, Dr Jennifer and Long, Dr Deliang and Cronin, Professor Lee |
Authors: | Zheng, Q., Vilà-Nadal, L., Lang, Z., Chen, J.-j., Long, D.-L., Mathieson, J. S., Poblet, J. M., and Cronin, L. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | Journal of the American Chemical Society |
Publisher: | American Chemical Society |
ISSN: | 0002-7863 |
ISSN (Online): | 1520-5126 |
Published Online: | 23 January 2018 |
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