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Investigations of Stimuli-Responsive Platinum(II) Salts

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2017, PhD, University of Cincinnati, Arts and Sciences: Chemistry.
Vapochromic materials have attracted attention due to their potential use in chemical sensing and chemical storage applications. In particular, the development of vapochromic materials, which exhibit pronounced color changes upon exposure to volatile organic compounds (VOCs), is advantageous because these materials can be used as visual indicators for hazardous chemicals. Stacked square-planar d8-electron metal complexes are especially attractive for sensing applications, because the colors and luminescence properties of these materials are strongly dependent on non-covalent metal-metal interactions, which are perturbed by vapor absorption/desorption. This spectroscopic response potentially can be used as a visual indicator for the presence of specific VOCs. However, there remain deficiencies in our understanding of the properties of vapochromic materials, and these are preventing the development of effective strategies for incorporating vapochromic materials in sensing devices. Notably, it is not fully understood how vapochromic materials absorb/desorb vapors. Moreover, the discovery of vapochromic materials tends to be serendipitous, and little is known about how to modulate their properties. With these difficulties in mind we became interested in characterizing vapochromic properties of [Pt(tpy)Cl]+ salts (tpy=2,2';6',2"-terpyridine). Chapter 2 takes a deeper look at the fate of the [Pt(tpy)Cl](PF6) during sorption/desorption to acetonitrile. The spectroscopic, XRPD, SEM, and optical images reveal surprising complexity in the vapochromic response, including significant vapor-induced mechanical effects. Chapter 3 shows proof-of-concept that vapochromic materials can be used to detect VOCs iii dissolved in water. Specifically, [Pt(tpy)Cl](PF6) responds to acetonitrile in water, and that response is compared to the response of [Pt(tpy)Cl](PF6) to acetonitrile vapor. Chapter 4 shows the hysteresis in the response of [Pt(tpy)Cl](ClO4) to water vapor. Chapter 5 describes a mechanochromic system that was fully characterized by single crystal X-ray diffraction. This is the first case mechanochromism in a platinum(II) system in which the structural basis for the effect has been fully determined. Chapter 6 describes the response of [Pt(tpy)Cl](PF6) to nitric acid in water. Interestingly, an intermediate is detected during the anion exchange reaction.
William Connick, Ph.D. (Committee Chair)
Neil Ayres, Ph.D. (Committee Member)
Michael Baldwin, Ph.D. (Committee Member)
138 p.

Recommended Citations

Citations

  • Norton, A. E. (2017). Investigations of Stimuli-Responsive Platinum(II) Salts [Doctoral dissertation, University of Cincinnati]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1504781443162754

    APA Style (7th edition)

  • Norton, Amie. Investigations of Stimuli-Responsive Platinum(II) Salts. 2017. University of Cincinnati, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=ucin1504781443162754.

    MLA Style (8th edition)

  • Norton, Amie. "Investigations of Stimuli-Responsive Platinum(II) Salts." Doctoral dissertation, University of Cincinnati, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1504781443162754

    Chicago Manual of Style (17th edition)