Committee Members Information

• Ph.D. Advisor: Professor Mohamed Eddaoudi (KAUST Chemistry)
• External Examiner: Professor Nathaniel L. Rosi (Department of Chemistry, University of Pittsburg (USA)
• Committee Chair: Professor Ingo Pinnau (KAUST Chemical Engineering)
• 4th Committee Member:  Professor Nikkolas Hadjichristidis (KAUST Chemistry)
• 5th Committee Member:  Professor Guillaume Maurin (University of Montpellier (France).

Developing novel materials for energy and environmental sustainability remains a central goal of materials science. Among the most promising candidates are metal-organic frameworks (MOFs), a versatile class of crystalline porous materials distinguished by their modularity, high surface areas and structural tunability. Reticular chemistry has emerged as a powerful strategy for the rational design of such materials by enabling the deliberate assembly of metal clusters and organic linkers into predetermined topologies with targeted pore architectures and functions. Expanding the diversity of accessible framework structures, however, remains a major challenge due to the limited availability of suitable blueprint nets. To address this limitation, a merged-net design strategy has been developed that balance design ability and complexity. Within this framework, relationships among 53 edge-transitive nets were analyzed to construct a compatibility map that identifies viable net pairs, enabling the generation of 353 merged-net topologies and the proposal of more than 100 candidate MOF architectures. 

This dissertation focuses on the experimental realization and validation of these predicted structures. Through the targeted synthesis and characterization of representative materials, the feasibility of this merged-net strategy is experimentally demonstrated, providing direct proof-of-concept for the realization of complex framework architectures. To evaluate their functional potential, we further perform high-throughput grand canonical Monte Carlo screening on more than 100 MOF platforms for gas storage, revealing the interplay between topology, pore architecture, and working capacity, and identifying high-performing candidates. 

Beyond structure generation, controlling order within disordered positions remains a major challenge. Using the merged-net strategy, we achieved precise control over both ordered and disordered arrangements by assigning different roles to each net one maintaining the framework, the other guiding linker ordering. This allowed us to position a tetratopic rectangular linker within hexagonal nodes and identify 33 uniform configurations from over 43 million possibilities, corresponding to four distinct topologies. One of these was successfully synthesized, confirming the accuracy of our predictions. Theoretical studies support the feasibility of the remaining three, and notably, the ordered structure shows enhanced methane storage performance compared to conventional designs. 

In parallel, we uncover discrete structural bistability in MOFs, where frameworks constructed from identical building units and topology resolve into distinct, non-interconverting states with differentiated pore geometries and adsorption properties. Together, these results establish reticular chemistry as a powerful platform for expanding MOF design space, extracting order from disorder and tailoring pore architectures for clean-energy storage and separation.