Abstract

Reticular chemistry stands as a formidable tool in the precise design of metal-organic frameworks (MOFs) tailored for specific properties and applications. Its significance in materials science has grown substantially, particularly for its effectiveness in developing MOFs suited to a wide range of applications. This dissertation delves into the synthesis of novel MOFs using cutting-edge techniques in reticular chemistry, with a particular emphasis on the Molecular Building Block (MBB) approach. By meticulously selecting both inorganic and organic components, we have successfully synthesized a series of titaniumbased heterometallic MOFs, with a focus on those exhibiting soc topology, which demonstrate distinct structural and functional attributes.

Moreover, this research explores the innovative synthesis of MOFs utilizing MXenes, a groundbreaking class of two-dimensional materials, as metal precursors. Specifically, the study successfully fabricates a vanadium-based MOF with a nanosheet morphology (V-PMOF) by integrating V₂CTₓ MXene with H₂TCPP ligands, leading to enhanced structural and functional properties, including significantly improved proton conductivity. Additionally, we highlight a novel synthesis approach for titanium-based MOFs derived from Ti₃C₂ and Ti₂C MXenes. The research also addresses the inherent challenges in the direct synthesis of titanium-based MOFs, which stem from titanium’s high reactivity and its strong affinity for oxygen. We thoroughly examine these synthesis challenges and explore optimization strategies, both in the mix-metal approach, where titanium is combined with a softer metal, and in the synthesis of Ti-MXene-derived MOFs.

Further, the dissertation investigates the application of reticular chemistry to customize fcu-MOFs for advanced applications. The study centers on the 12-connected fcu topology, leveraging the adaptability of metal selection and linker modification to fine-tune pore sizes, thereby optimizing gas separation efficiency. This research demonstrates how the intrinsic structural properties of MOFs can be strategically enhanced through defect engineering and the incorporation of specific linkers such as cubanedicarboxylic acid. Additionally, we explore the development of luminescent MOFs for use in X-ray scintillators and high-speed optical wireless communication systems. The findings highlight the versatility of fcu-MOFs in both gas separation and advanced communication technologies, paving the way for future innovations in these areas. 

In conclusion, this work makes a significant contribution to the expanding field of MOF chemistry and opens new pathways for the design and application of bespoke MOFs in innovative technologies.