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Engineering chiral molecular switches

Posted on:2005-03-23Degree:Ph.DType:Thesis
University:New York UniversityCandidate:Barcena, Homar SFull Text:PDF
GTID:2458390008990348Subject:Chemistry
Abstract/Summary:
Recent advances in technology promise the development of computers and data storage systems miniaturized at the nanometer scale. Controlling molecular motion has been the subject of many scientific inquiries, and the recent demands for molecular-scale energy transport, conversion, and detection highlights the importance of studying molecular processes at this scale. In this era of molecular engineering, this manuscript focuses on developing single-molecule switches. These switches are electrochemically triggered to promote a conformational change in the molecule, which is detected by circular dichroism spectroscopy (CD).; Copper complexes of N,N-dialkyl methionine tripodal ligands show inversion of chiroptical signal upon reduction and oxidation of the metal center. In order to facilitate the development of these switches towards functional devices, the mechanism and rate of switching is examined in Chapter 2. Synthesis of the sulfoxide of the ligand, spectroelectrochemistry, and cyclic voltammetry indicate a square scheme mechanism, while scanning electrochemical microscopy and stopped-flow CD establish switching occurs on the millisecond timescale.; A new molecular switch is described in Chapter 3. This switch also demonstrates interesting chiroptical behavior, as it can be triggered by the addition of protons, as well as by electrons. The information gleaned from these studies is applied here to design future generation of switches.; Two of these exploratory models are described in Chapter 4, engineered for greater stability towards air. Synthesis of N,N-dialkylated methionine derivatives were effected by reductive amination. A procedure involving alkylation of a bromoester with a secondary amine was also developed, concomitant to the discovery of a facile method to make bis(pyridylethyl)amine. Preliminary results show promising conformational switching upon changing the metal center, warranting future development of the ligands to incorporate stable chromophores.; Finally, a summary of the achievements from this study is given in Chapter 5. A detailed account of the experimental procedure is given in Chapter 6, along with the spectra of new and relevant compounds.
Keywords/Search Tags:Molecular, Switches, Chapter
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