Structural investigation of nanocrystalline reticular materials through 3D electron diffraction

The research presented in the following thesis focuses on the synthesis and characterisation of novel nanocrystalline reticular materials. Various organic and metal-organic, porous 2D and 3D crystalline compounds are reported and discussed, including Metal-Organic Frameworks (MOFs), comprising metal ions or clusters held together by organic linkers, and Supramolecular Organic Frameworks (SOFs), which derive from the self-assembly of organic tectons through non-covalent interactions. These materials have been obtained employing a variety of synthetic methods, ranging from solvothermal to mechanochemical synthesis. The crucial role of 3D electron diffraction (3D ED) analysis in the structural investigation of the reported compounds is demonstrated throughout each chapter. Diverse data collection protocols and instrumental setups dedicated to this emerging crystallographic technique are herein reported, as well as the use of a novel electron diffractometer. In particular, Chapter 4 gives a significative example of the 3D ED potential by introducing a novel approach for the structural investigation of mechanochemically-synthesized reticular materials. Chapter 5 elucidates the dynamic behaviour of SOFs based on the rigid organic tecton tetra-4-(4-pyridyl)phenylmethane (TPPM). Chapter 6 describes how TPPM and paddle-wheel complexes of Copper(II) can be combined to yield a series of highly interpenetrated MOFs that exhibit diamond-like networks. The functionalisation of these networks by the introduction of fluorinated secondary building units (SBUs) is also discussed, along with the effect this can have on the properties of the materials. Lastly, Chapter 7 discusses the synthesis and characterization of 2D and 3D bismuth-based reticular materials. This part of the work has been carried out at Stockholm University, under the supervision of Prof. Andrew Kentaro Inge.