Date of Completion

6-30-2017

Embargo Period

6-30-2017

Major Advisor

Christian Brückner

Associate Advisor

Mark Peczuh

Associate Advisor

Amy Howell

Associate Advisor

Edward Neth

Field of Study

Chemistry

Degree

Doctor of Philosophy

Open Access

Open Access

Abstract

This thesis focuses on the development of new synthetic methodologies toward porphyrinoids with properties designed for various applications. Among the chromophores studied are the quinoline‑annulated porphyrins, a relatively unexplored class of p-extended porphyrinoids that absorb light in the near-infrared region (NIR). Another class studied are the pyrrole-modified porphyrins (PMPs), (hydro)porphyrin analogues containing a non-pyrrolic building block.

The synthesis of chlorin and chlorin-analogues of the quinoline-annulated porphyrins are described that are characterized by even more red-shifted optical spectra than regular quinoline-annulated porphyrins (Chapter 2). The NIR-emitting platinum(II) complexes of the quinoline-annulated porphyrins suggest potential in vivo O2 sensing applications (Chapter 3). Photophysical studies of the free-base quinoline-annulated porphyrins, along with ex vivo photoacoustic imaging (PAI) studies, revealed their promise as novel PAI contrast agents. The preparation of water-soluble derivatives and their evaluation in vivo for the PAI imaging of an implanted tumor in a mouse model is described (Chapter 4).

A new methodology toward hitherto inaccessible PMPs incorporating medium-sized rings is also delineated (Chapter 5). Initial experiments toward this class of PMPs resulted in a serendipitous finding of a more efficient route toward a known class of PMPs containing an imidazolone moiety, the porpholactams. The conversion of the porpholactam to a number of chelator-substituted imidazoloporphyrins toward the goal of generating metal-ion chemosensors for the selective and sensitive detection of M2+ cations is also delineated (Chapter 6).

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