SHAPE-SELECTIVE GROWTH AND ORGANIZATION OF INORGANIC NANO-MATERIALS WITHIN PORES OF REUSABLE CRYSTALLINE SUPRAMOLECULAR MATRIXES – InsidePores

InsidePores is an exploratory project dedicated to the optimization of the chemical procedures allowing the preparation of shape and size controlled nano-objects, either as composites (NP@matrixe) or free materials. It focuses primarily on ZnO and targets a material that will exhibit only the excitonic emission in the UV energy range (desirable for UV laser and blue-LED applications). An extension concern metallic NPs of noble metals (Ag, Au...) for the elaboration of plasmonic nanocomposite metamaterials.

work in progress

will depend on the sucess of the ongoing work

Chem. Eur. J. 2017, 23, 11818-11826 dx.doi.org/10.1002/chem.201701732
G. Mouchaham, N. Roques, W. Khodja, C. Duhayon, Y. Coppel, S. Brandès, T.s Fodor, M. Meyer, J.-P. Sutter
Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into its Affinity for Acidic Molecules in Solution

InsidePores proposes an original and low cost approach to elaborate nano-structured inorganic materials (NPs) by a solution process. Compared to existing synthetic methodologies, the novelty relies on the use of dedicated porous supramolecular materials acting as matrixes for template-assisted growth of the NPs. These porous solids are sustained by H-bonds, and are highly crystalline with perfectly defined micropores. We aim at using the confined space within the supramolecular template to grow metal and metal-oxide materials, which size, shape, and spatial organization will be controlled by the host's porosity. Furthermore, the formed NPs can be easily freed by dissolution of the matrix. This synthesis process avoids the use of ligands/surfactants as growth-controlling agents; hence we anticipated NPs with defect(ligand)-free surfaces. An additional interest of this approach concerns the recycling of the matrix. Indeed, upon dissolution, it just dissociates to its molecular components, and can be crystallized back and re-involved in a NP synthesis.
An essential step of the overall process is the insertion of the molecular precursors of the NPs into the porosity of the matrix. To achieve efficient and fast loading, it is desirable that the incoming guests have weak interactions with the matrix. For this reason, the selected matrixes have the walls of their channels functionalized by chemical groups able to form such weak links with the guests. Two existing robust porous supramolecular architectures have been identified as good candidates for acting as matrixes. They possess either 1-D channels or channels interconnected in 2-D, which are characterized by a pore diameter of 1.2 nm. Moreover, their building units can be modified without altering the material's structures, hence allowing modulation of the chemical function displayed by the channels.
InsidePores is an exploratory project dedicated to the optimization of the chemical procedures allowing the preparation of shape and size controlled nano-objects, either as composites (NP@matrixe) or free materials. It focuses primarily on ZnO and targets a material that will exhibit only the excitonic emission in the UV energy range (desirable for UV laser and blue-LED applications). An extension concern metallic NPs of noble metals (Ag, Au...) for the elaboration of plasmonic nanocomposite metamaterials.