Date of Award
Doctor of Philosophy (PhD)
Coordination-driven self-assembly is an attractive strategy for constructing thermodynamically stable supramolecular coordination complexes, ranging from discrete metallacycles and cages to infinite coordination polymers and metal-organic frameworks for a variety of applications.
Chapter 1 discusses strategies for preparing supramolecular charge-transfer π-donor/acceptor assemblies and their potential applications.
Chapter 2 demonstrates that tricomponent self-assembly method, which was believed to yield 3D-cages, based on tetrapyridyl porphyrin (M’TPP, M’ = Zn or H2), dicarboxylate ligands (XDC), and caped cis-Pt(II) corners, actually yields 2D-bowties featuring an M’TPP core and two parallel XDC linkers held together by four heteroligated PtII(N,O) corners. The 2D-bowties showed selective recognition towards highly π-acidic molecules via strong π-D/A CT interactions. This work emphasizes the importance of accurate characterization to properly depict the structure-property relationships of supramolecular systems.
Chapter 3 illustrates how discrete π-donor/acceptor (π-D/A) stacks can be formed using a preorganized 3D cage having two parallel tetra(4-carboxyphenyl)-Zn-porphyrin (ZnTCPP) faces connected by four bis Pd-clips. The π-donor ZnTCPP faces engage intercalated π-acid molecules in strong π-D/A charge transfer interactions. This work demonstrates how the strong π-D/A charge transfer interactions can be used to improve the optical changes and conductivity of the assembly.
Chapter 4 describes the use of a cis-Pd capped complex to prepare a naphthalene diimide (NDI) metallocycle. The single crystal structure of the metallocycle revealed the presence of non-covalent anion-π interactions between the NDI and counterions, which endowed its anion recognition capabilities. Further analysis showed that the metallocycle underwent anion exchange processes in a single-crystal fashion without any structural changes.
Benavides, Paola, "Supramolecular pi-Donor/Acceptor Arrays Based on Redox-Active Metal-Organic Coordination Assemblies" (2023). All Dissertations. 3291.
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