Graduation Year
2022
Document Type
Dissertation
Degree
Ph.D.
Degree Name
Doctor of Philosophy (Ph.D.)
Degree Granting Department
Chemistry
Major Professor
Jianfeng Cai, Ph.D.
Committee Member
Edward Turos, Ph.D.
Committee Member
Kirpal Bisht, Ph.D.
Committee Member
Manh-Huong Phan, Ph.D.
Keywords
Metallo-Polymers, Self-assembly, Supramolecule, Terpyridine
Abstract
By studying coordination complexes in nature, such as chlorophyll, heme, and Enterobacter, we have learned that the structures of coordination complexes are closely related to their functions. However, it remains a challenge to achieve elaborate structures and sophisticated functions of complexes through synthetic methods. In the supramolecular chemistry field, coordination-driven self-assembly as a bottom-up approach are used to construct diverse supramolecules with well-defined structures and desired functions. The ways to achieve the goal including (1) rearranging components through coordination; （2）linking metal ions and organic frameworks to complete energy transfer; (3) converting between assembly and disassembly due to detection of stimuli. Among diverse organic ligands, tpy is widely utilized as a tridentate chelate for its feasible synthesis and flexibility to coordinate with different metal ions ranging from transition- p-block (main group), d-block (transition metal) as well as f-block (lanthanide and actinides). At the same time, in order to give full play to the advantages and uniqueness, the modification of tpy is necessary in most case. In addition, the metal does the tricks, by simply switching the metal ion, variation of stabilities and optoelectronic properties of the metallo-supramolecular assemblies can be achieved. Lanthanide metals embed large atomic radius, so they are able to take higher coordination numbers which provide possibility for designing new architectures.In this dissertation, multiple-step synthesis was explored and demonstrated towards ligands. Moreover, various metal ions including transition metals and lanthanides have been successfully combined into the supramolecules (macrocycle, polymers, cages) which bring fascinating features e.g., aggregation induced effect, isomerism identifiability, unique fluorescence properties. In chapter 1, the concept and development of tpy-based coordination-driven discrete supramolecular architectures, metallo-supramolecular polymers are introduced. Then, the research progress and applications of tpy derivatives related to supramolecules are reviewed. From the perspective of research gap, the idea of project design is proposed. In chapter 2, we introduced an aggregation-induced emission effect into a supramolecular fluorescence system by restriction of intramolecular rotation through the self-assembly behavior. The emissive properties successfully remain in both solution and aggregation states. In chapter 3, we successfully synthesize metallo-supramolecular polymers through the incorporation of conventional polymerization and coordination. 2n arrangements of repeating patterns are expected to form and able to be visualized. As for chapter 4, we design a supramolecular cage assembled by substituted terpyridines and lanthanide ions which produce unique strong emissions. Characterization of those architectures includes 1D and 2D NMR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), traveling-wave ion mobility mass spectrometry (TWIM-MS), matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), transmission electron microscopy (TEM), and scanning tunneling microscopy (STM). Photophysical, electrochemical properties, and dynamic features of metallo-supramolecules have been investigated as well.
Scholar Commons Citation
Yan, Yu, "Self-Assembly of Metallo-Supramolecules Based on Terpyridine and its Derivatives" (2023). USF Tampa Graduate Theses and Dissertations.
https://digitalcommons.usf.edu/etd/10462
