Synthesis, Characterization, and Applications of Visible Light Active Metal-Organic Frameworks

Understanding how crystalline materials are assembled is important for the rational design of metal-organic frameworks (MOFs). Controlling their formation can allow researchers to streamline the synthesis of new materials as well as control their properties for targeted applications. In the first chapter of this thesis we report the construction of two 3-dimensional TbIII based MOFs (SION-1 and SION-2). Here, SION-2 acts as a metastable MOF and intermediate phase that partially dissolves and transforms into the thermodynamically stable MOF, SION-1. This chemical transformation occurs in a DMF/water solvent mixture, and is triggered when additional energy is provided to the reaction. In situ studies reveal the partial dissolution of the metastable phase after which the MOF components are reassembled into the thermodynamically stable phase. The marked difference in thermal and chemical stability between the kinetically and thermodynamically controlled phases is contrasted by their identical chemical building unit composition. Following the understanding of this transformation, an isostructural family of SION-1 and SION-2 had been constructed using lanthanide metal salts, where LnIII-SION-1 is comprised of Ce, Nd, Eu, Gd, Tb, Dy, Ho, Er, Yb and Lu and LnIII-SION-2 is formed using Ce, Nd, Eu, Gd, Tb and Yb. The electronic properties of lanthanide based MOFs have not been extensively studied due to the general cognizance that LnIII ions behave as isolated free ions as their 4f orbitals do not contribute to bonding. Here, we systematically studied the electronic properties (UV-vis) of LnIII-SION-1 and LnIII-SION-2 and show that the higher the intensity of this absorption band in LnIII-SION-1 is due to the better overlap between Ln(5d) and ligand(pi*) orbitals and reveals that the lowest unoccupied crystalline orbitals are dispersed over an energy range and can be considered as a conduction band. We validated this observation by the non-linear I-V curves collected on CeIII- and YbIII-SION-1, both of which display dielectric properties. In the second chapter of this thesis, we rationally design a novel biologically derived MOF featuring unobstructed Watson-Crick faces of Ade pointing towards the MOF cavities. We show, through a combined experimental and computational approach, that Thy molecules diffuse through the pores of the MOF and become base-paired with Ade. The Ade-Thy pair binding at 40-45% loading reveals that Thy molecules are packed within the channels in a way that fulfill both the Woodward-Hoffmann and Schmidt rules, and upon UV irradiation, Thy molecules dimerize into Thy<>Thy. This study highlights the utility of MOFs as nanoreactors for the synthesis of molecules that are otherwise difficult. Concluding this thesis, a biologically derived multimodal sensor MOF is synthesized and a formed into a device. The MOF, SION-9, is comprised of Ade and a porphyrin based ligand, and has tuneable conductive properties ranged from 2.69-4.20 x 10-8 - 7.43-7.34 x 10-6 S/cm. SION-9 is sensitive to both pressure and temperature simultaneously, and demonstrated both fast response times (< 60 ms) and a long shelf life (> 6 months).

Smit, Berend
Stylianou, Kyriakos
Lausanne, EPFL

 Record created 2019-10-23, last modified 2019-10-23

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