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Mircea Dincă. Park, Sarah Sunah Massachusetts Institute of Technology. Department of Chemistry. Massachusetts Institute of Technology. Department of Chemistry 2018-03-02T22:21:40Z 2018-03-02T22:21:40Z 2017 2017 http://hdl.handle.net/1721.1/113983 1023628672 Thesis: Ph. D. in Inorganic Chemistry, Massachusetts Institute of Technology, Department of Chemistry, 2017. Cataloged from PDF version of thesis. Vita. Includes bibliographical references (pages 129-136). This thesis focused on designing, characterizing and understanding the electronic or ionic behavior of electron- or ion-conducting metal-organic frameworks (MOFs). Chapter 1 gives a general introduction for electron- or ion-conducting MOFs, including a review of the reported materials exhibiting such behavior. Chapter 2 describes new MOFs designed using through-space charge transport strategies, as introduced in Chapter 1. Chapter 2 discusses four isostructural materials of general formula M2(TTFTB) (M = Mn, Co, Zn, and Cd), which exhibit infinite helical TTF stacks and reveal a correlation between the shortest intermolecular S ... S interaction among neighboring TTF cores and their single crystal conductivity. These results are the first demonstration of tuning intrinsic electrical conductivity of a MOF and provide a systematic blueprint for the design of throughspace charge transporting MOFs. Chapter 3 details the study of ligand-directed topologies in the material Mg₂H₆(H₃O)(TTFTB) 3 (MIT-25), obtained from H₄TTFTB, a ligand with a high propensity toward [pi]-stacking. Because understanding intermolecular [pi]-stacking interactions is important for designing through-space charge transport materials, we studied the significance of how the organic secondary building unit (SBU), which is energetically competitive with the formation of common inorganic SBUs, can also define MOF topology. Chapters 4 and 5 demonstrate examples of MOFs as ionic conductors. In Chapter 4, the proton conductivity of MIT-25 is studied. Owing to its large proton content and compositionally integral hydronium ion, MIT-25 exhibits an strongly hydrophilic environment that facilitates proton conduction. Lastly, Chapter 5 reports a Cu(II)-azolate MOF (MIT-20) with cylindrical pores, which undergoes a reversible single crystal-to-single crystal transition between neutral and anionic phases upon reaction with stoichiometric amounts of halide or pseudohalide salts. By utilizing this transformation, halide/pseudohalide anions are bound to the metal centers and become stationary, while the cations move freely within the one-dimensional pores, giving rise to single-ion Li+, Na+, or Mg²+ solid electrolytes. by Sarah Sunah Park. Ph.D. in Inorganic Chemistry 141 pages eng Massachusetts Institute of Technology MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission. http://dspace.mit.edu/handle/1721.1/7582 Chemistry. Electron- and ion-conducting metal-organic frameworks Thesis application/pdf false Publication unknown unknown <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="338dea81-c592-4631-bb39-c9cb07cad836"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Language>eng</Language> <Title>Electron- and ion-conducting metal-organic frameworks</Title> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2017</PublicationDate> <Authors> <Author> <DisplayName>Park, Sarah Sunah</DisplayName> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <DisplayName>Massachusetts Institute of Technology</DisplayName> <OrgUnit /> </Publisher> </Publishers> <License>http://dspace.mit.edu/handle/1721.1/7582</License> <Keyword>Chemistry.</Keyword> <Abstract>This thesis focused on designing, characterizing and understanding the electronic or ionic behavior of electron- or ion-conducting metal-organic frameworks (MOFs). Chapter 1 gives a general introduction for electron- or ion-conducting MOFs, including a review of the reported materials exhibiting such behavior. Chapter 2 describes new MOFs designed using through-space charge transport strategies, as introduced in Chapter 1. Chapter 2 discusses four isostructural materials of general formula M2(TTFTB) (M = Mn, Co, Zn, and Cd), which exhibit infinite helical TTF stacks and reveal a correlation between the shortest intermolecular S ... S interaction among neighboring TTF cores and their single crystal conductivity. These results are the first demonstration of tuning intrinsic electrical conductivity of a MOF and provide a systematic blueprint for the design of throughspace charge transporting MOFs. Chapter 3 details the study of ligand-directed topologies in the material Mg₂H₆(H₃O)(TTFTB) 3 (MIT-25), obtained from H₄TTFTB, a ligand with a high propensity toward [pi]-stacking. Because understanding intermolecular [pi]-stacking interactions is important for designing through-space charge transport materials, we studied the significance of how the organic secondary building unit (SBU), which is energetically competitive with the formation of common inorganic SBUs, can also define MOF topology. Chapters 4 and 5 demonstrate examples of MOFs as ionic conductors. In Chapter 4, the proton conductivity of MIT-25 is studied. Owing to its large proton content and compositionally integral hydronium ion, MIT-25 exhibits an strongly hydrophilic environment that facilitates proton conduction. Lastly, Chapter 5 reports a Cu(II)-azolate MOF (MIT-20) with cylindrical pores, which undergoes a reversible single crystal-to-single crystal transition between neutral and anionic phases upon reaction with stoichiometric amounts of halide or pseudohalide salts. By utilizing this transformation, halide/pseudohalide anions are bound to the metal centers and become stationary, while the cations move freely within the one-dimensional pores, giving rise to single-ion Li+, Na+, or Mg²+ solid electrolytes.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>