Assembly of inorganic [Mo2S2O2](2+) panels connected by selenite anions to nanoscale chalcogenide-polyoxometalate clusters

作者：Zang, Hong-Ying; Chen, Jia-Jia; Long, De-Liang; Cronin, Leroy^*; Miras, Haralampos N.^*

来源：Chemical Science, 2016, 7(6): 3798-3804.

DOI：10.1039/c5sc04944j

• METAL-ORGANIC FRAMEWORK
• SUPRAMOLECULAR CHEMISTRY
• PROTON CONDUCTIVITY
• BUILDING-BLOCK
• EVOLUTION
• COMPLEX
• BINDING
• FAMILY
• MATTER
• WHEEL

We describe how supramolecular assembly, mediated by control of the ratio of the hetero-atoms in the units [Mo2S2O2](2+) and SeO32- leads to the formation of new types of building blocks, [(Mo2O2S2)(3)(OH)(4)(H2O)(6)(SeO3)] = {Mo-6} and [(Mo2O2S2)(2)(OH)(2)(H2O)(4)(SeO3)] = {Mo-4} which are linked in an type of inorganic 'panelling' to the assembly of a range of new clusters 1-3 with the general formula {(Mo2O2S2)(x)(OH)(y)(SeO3)(z)(H2O)(w)}(n-), where x, y, z, w, n = [8, 0, 20, 8, 24] for 1, [14, 14, 17, 8, 20] for 2 and [8, 8, 8, 0, 8] for 3. Cluster 1, a rare example of inorganic cryptand, exhibits an elliptical "endo" motif defining an anisotropic ellipse with the dimensions 1.7 x 1.0 nm, with pores ranging from 5.3 to 6.4 angstrom and site selective cation recognition properties; cluster 2 exhibits an "exo" structural motif constructed by 3 x {Mo-6} and 2 x {Mo-4} panels spanning a cross shape 2.4 x 2.0 nm and cluster 3 a ring shaped structure of a 1.5 nm in diameter. The control of endo vs. exo topology as a function of the Se:Mo ratio is reflected to the difference in surface area of ca. 500 angstrom(2) between clusters 1 and 2 intermolecular interactions and proton conduction properties, and this work shows that very simple synthetic parameters can critically change the structure and properties of all-inorganic nanoscale chalcogenide-polyoxometalates.

• 出版日期2016
• 单位东北师范大学