Porphyrinoids with Designed Properties
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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).