Graduation Year


Document Type




Degree Name

Doctor of Philosophy (Ph.D.)



Degree Granting Department


Major Professor

Mohamed Eddaoudi, Ph.D.

Committee Member

Shenqian Ma, Ph.D.

Committee Member

Abdul Malik, Ph.D.

Committee Member

Juergen Eckert, Ph.D.

Committee Member

Lukasz Wojtas, Ph.D.


cavity, coordination chemistry, MOMs, porosity, ZMOFs


Metal-Organic Materials (MOMs) represent an important division of coordination chemistry. They are self-assembled through the linking of metals with organic ligands. They gained their spotlight among scientists for their aptitude for design and facile synthesis via their multi-component coordination, and their readiness to functionalization. MOMs have been targeted for specific industrial and environmental applications such as gas storage, catalysis and CO2 sequestration.

Throughout the past decade, studies have been conducted to develop systematic approaches toward the design and synthesis of functional MOMs. Their synthesis from targeted building units has facilitated their rational design and functionalization. The Molecular Building Block (MBB) approach was first developed to direct the design of MOMs from preset building blocks with specific connectivity amenable to form the overall MOM structure with the desired topology. These building blocks are easily constructed in situ through the chelation of multifunctional ligands (i.e, carboxylic acid, amine, etc) to single ion or cluster metals such as dinuclear copper paddlewheel, and basic zinc acetate. As complexity and applications for MOMs increased, a new approach was developed through the utilization of Supermolecular Building Blocks (SBBs) for the assembly of more complex and higher connected MOM structures. The SBB approach is implemented through the formation of highly coordinated metal-organic polyhedra (i.e, small rhombihexahedron, cuboctahedron, etc) which are further linked by organic ligands to construct functional porous materials with the desired net topology.

In this work, we focus on the implementation of a new design approach based on utilizing targeted [M(R-BDC)]n 2D layers as building blocks, i.e Supermolecular Building Layers (SBLs). We target well-known 2D layers that are amenable to pillaring through organic building blocks with specific geometries (i.e quadrangular, hexangular) in order to rationally design and synthesize functional porous metal-organic materials. These SBLs are derived from multifunctional ligands capable of both directing the formation of the 2D layers and pillaring to construct the overall targeted 3D structures with the desired topology (i.e, tbo-MOMs, eed-MOMs, mmm-MOMs, bor-MOMs, and eef-MOMs). Ultimately, we construct isostructural, and isoreticular materials which show potential for many applications such as gas storage, gas separation, and catalysis. These materials have been targeted through the rational choice of specific ligands and proper metals which we recognized to have the capability and the functionality to direct the construction of the desired functional materials and to reach our research goals.

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