Self-organized microporous structures based on a series of surfactant-encapsulated polyoxometalate complexes(SECs) have been prepared by using ordered condensed droplets as a template. Among these structures,ordered honeycomb structures were obtained and characterized in detail by taking (DODA)
12H[Eu(SiW
11O
39)
2](SEC-1) as an example. Optical microscope, atomic force microscopic, and scanning electron microscopicmeasurements confirmed the formation of three-dimensional microporous structure, in which the top surfaceshows a highly ordered honeycomb structure. As compared to common solvent-casting films, the correspondinghoneycomb films are more hydrophobic and possess more ordered lamellar structures. Both the wettabi
lityand the size of SECs exert significant influence on the formation of microporous structures. The properhydrophobicity of SECs was proposed to be an essential factor for the formation of honeycomb films, andlarge-sized SECs are favorable for the fabrication of highly ordered honeycomb structures. The conditionsfor the formation of different surface morphologies have been discussed in terms of the contact angle ofSECs at the interface between water and chloroform, and a contact angle s
lightly greater than 90
is foundto be a prerequisite for the formation of honeycomb structures. The results reported in this paper not onlyhelp to further comprehend the mechanism of the formation of honeycomb structures, but also provide someguidance for the design of ordered microporous films based on organic/inorganic hybrid materials, exemp
lifiedby the organic/nanoparticle complexes.