Exploring the programmable assembly of a polyoxometalate− organic hybrid via metal ion coordination

Yin, P., Li, T., Forgan, R.S. , Lydon, C., Zuo, X., Zheng, Z.N., Lee, B., Long, D. , Cronin, L. and Liu, T. (2013) Exploring the programmable assembly of a polyoxometalate− organic hybrid via metal ion coordination. Journal of the American Chemical Society, 135(36), pp. 13425-13432. (doi: 10.1021/ja404777g)

Abstract

The conformational flexibility and programmed assembly of a dumbbell-shaped polyoxometalate–organic hybrid molecule comprising two Dawson-type polyoxometalates linked by a 2,2′-bipyridine unit, which can be coordinate to metal ions, in this case of Zn2+, are described. SAXS, UV/vis, and NMR spectroscopic techniques confirm that the hybrid molecules exist as the trans dumbbell in metal-ion-free solutions and can be reversibly transformed into the cis dumbbell through coordination upon the addition of ZnCl2 into a DMSO solution containing the hybrid. Subsequent addition of EDTA reverses the switching process by extracting the Zn2+ cations from the hybrid. During the interchange process between trans and cis dumbbells, a further reorganization of the hybrid molecules occurs through bond rotation to minimize steric clashes between the polyoxometalate subunits, in order to stabilize the corresponding dumbbell conformation. The Zn2+-controlled conformational transformation of the hybrid can be further utilized to manipulate the hybrid’s solvophobic interaction-driven self-assembly behavior in the metal-ion driven reversible formation of 140 nm sized vesicles, studied by laser light scattering techniques.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Lydon, Miss Claire and Forgan, Professor Ross and Long, Dr Deliang and Cronin, Professor Lee
• Authors: Yin, P., Li, T., Forgan, R.S., Lydon, C., Zuo, X., Zheng, Z.N., Lee, B., Long, D., Cronin, L., and Liu, T.
• Subjects: Q Science > QD Chemistry
• 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