Structure-Property Relationship Studies of Electrically Conductive Metal-Organic Framework Materials
Date of Award
5-2024
Document Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
Department
Chemistry
Committee Chair/Advisor
Sourav Saha
Committee Member
Stephen Creager
Committee Member
William T. Pennington
Committee Member
Shiou-Jyh Hwu
Abstract
Electrically conductive metal-organic frameworks (EC-MOFs) are among the most promising materials due to their tunable structures, properties, and diverse functions. However, the lack of comprehensive understanding of their structure-property relationship hinders the development of EC-MOFs. My dissertation focuses on the design, construction, and structure-property relationship studies of EC-MOFs.
Chapter 1 describes how MOFs' structural features and compositions affect the electronic properties and demonstrates conductive mechanisms and the corresponding design strategies to develop EC-MOFs.
Chapter 2 describes the synthesis, characterization, electronic and optical properties of four novel alkali-metal-based (Na, K, Rb, and Cs) 3D-MOFs with continuous tetrathiafulvalene tetracarboxylate (TTFTC) π-stacks, systematicly demonstrating how the structures of MOFs, TTFTC•+ population and intervalence charge transfer (IVCT) interaction affected their band gaps and electrical conductivity.
Chapter 3 depicts a novel design strategy to enhance the bulk electrical conductivity of 2D graphitic MOFs by simultaneously remaining in-plane and enhancing out-of-plane charge transport through built-in alternating π-donor/acceptor stacks of electron-rich hexaaminotriphenylene (HATP) ligands and non-coordinatively intercalated π-acceptors hexacyano-triphenylene (HCTP) molecules.
Chapter 4 describes design, synthesis, and structure-property relationship studies of a novel 2D Cu3(HOTP)(HHTQ) MOF based on a π-donor 2,3,6,7,10,11-hexahydrotriphenylene (HOTP) ligand and a π-acceptor 2,3,7,8,12,13-Hexahydroxytricycloquinazoline (HHTQ) ligand. The resulting framework featured continuous out-of-plane π-D/A stacks and in-plane hexagonal π-D-A sheets, promoting through-space and through-bond charge transport, respectively, which gave rise to a bulk electrical conductivity than pristine Cu3(HOTP)2 and Cu3(HHTQ)2.
Finally, Chapter 5 describes the transformation of a collapse-prone, electrically insulating MOF-74 analog into structurally more stable, porous, and electrically conductive MOF/PEDOT composites.
Recommended Citation
Zhang, Shiyu, "Structure-Property Relationship Studies of Electrically Conductive Metal-Organic Framework Materials" (2024). All Dissertations. 3631.
https://tigerprints.clemson.edu/all_dissertations/3631
Author ORCID Identifier
https://orcid.org/0009-0008-5615-4654
Included in
Inorganic Chemistry Commons, Materials Chemistry Commons, Organic Chemistry Commons, Polymer Chemistry Commons