Parallel-stacked aromatic molecules in hydrogen-bonded inorganic frameworks

By precisely constructing molecules and assembling these into well-defined supramolecular structures, novel physical properties and functionalities can be realized, and new areas of the chemical space can be accessed. In both materials science and biology, a deeper understanding of the properties and exploitation of the reversible character of weak bonds and interactions, such as hydrogen bonds and pi-pi interactions, is anticipated to lead to the development of materials with novel properties and functionalities. We apply the hydrogen-bonded organic frameworks (HOFs) strategy to inorganic materials science using the cubic octamer of orthosilicic acid, [Si8O12][OH](8), as a building block, and find that various types of hydrogen-bonded inorganic frameworks (HIFs). We succeed in parallel pi-stacking pure benzene, thiophene, selenophene, p-benzoquinone, thiophene center dot p-benzoquinone, and benzene center dot p-benzoquinone polymers infinitely. These polymers interact via their pi-systems by taking advantage of the flexible pores of the three-dimensional nano-honeycomb HIFs, which consist of periodic wide and narrow segments. Hydrogen-bonded inorganic frameworks are porous structures that may lead to novel materials with unprecedented properties and functionalities. Here the authors report the solid-state structures of orthosilicic acid-based hydrogen-bonded inorganic frameworks that can encapsulate small unsaturated cyclic molecules such as benzene, which are found stacked in parallel.

Automated summary

By precisely constructing molecules and assembling them into well-defined supramolecular structures, novel physical properties and functionalities can be achieved, accessing new areas of the chemical space. The reversible character of weak bonds like hydrogen bonds and pi-pi interactions is anticipated to lead to the development of materials with novel properties and functionalities in both materials science and biology. Utilizing the hydrogen-bonded inorganic frameworks strategy, various types of hydrogen-bonded inorganic frameworks (HIFs) have been successfully produced, promising the creation of novel materials with unprecedented properties and functionalities.