Journal of the American Chemical Society
Journal of the American Chemical Society
5 years ago

Self-Sorting of Heteroanions in the Assembly of Cross-Shaped Polyoxometalate Clusters

Self-Sorting of Heteroanions in the Assembly of Cross-Shaped Polyoxometalate Clusters
Josep M. Poblet, Laia Vilà-Nadal, Jia-Jia Chen, De-Liang Long, Leroy Cronin, Qi Zheng, Jennifer S. Mathieson, Zhongling Lang
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.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b11982

DOI: 10.1021/jacs.7b11982

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