New Synthetic Strategies for Luminescent Platinum(II) and Iridium(III) Complexes



Journal Title

Journal ISSN

Volume Title



Luminescent transition metal complexes, specifically platinum and iridium complexes, have been widely employed in optoelectronic applications, as well as phosphorescent labels and sensors because of their favorable photophysical and electrochemical features. For their continued development and implementation in applications, careful control and optimization of photophysical and electrochemical properties of these complexes are a requisite, motivating studies on a more diverse range of structures. This dissertation is mainly focused on development of an unconventional ligand design strategies for Pt(II) and Ir(III) complexes. Chapter 1 introduces the concept that noncovalent Lewis acid-base interactions can modulate the excited-state properties of phosphorescent platinum compounds. Postsynthetic addition of borane Lewis acids to Lewis base decorated organoplatiunum chromophores induces significant changes in the optical and electrochemical properties, providing an approach more rapid and systematic than that offered by traditional covalent substituent modification. In Chapters 2–5, a new class of cyclometalated iridium complexes supported by acyclic diaminocarbene ancillary ligands is described, with a particular focus on improving the efficiency and stability of blue-emitting cyclometalated Ir(III) complexes. In a separate effort, in Chapter 6, a new synthetic approach to assemble Ir(III) and Pt(II) chromophores into Ir-Pt-Ir trimetallic complexes using the highly reactive cyclometalated iridium synthons is described. The supramolecular constructs were synthesized under mild conditions without extensive purification steps and could function as platforms for studying excited-state energy transfer dynamics.



Inorganic chemistry, Organometallic chemistry


Portions of this document appear in: Na, Hanah, Ayan Maity, and Thomas S. Teets. "Postsynthetic Systematic Electronic Tuning of Organoplatinum Photosensitizers via Secondary Coordination Sphere Interactions." Organometallics 35, no. 13 (2016): 2267-2274. And in: Na, Hanah, Ayan Maity, Rakib Morshed, and Thomas S. Teets. "Bis-Cyclometalated Iridium Complexes with Chelating Dicarbene Ancillary Ligands." Organometallics 36, no. 15 (2017): 2965-2972. And in: Na, Hanah, Ayan Maity, and Thomas S. Teets. "Bis-cyclometalated iridium complexes with electronically modified aryl isocyanide ancillary ligands." Dalton Transactions 46, no. 15 (2017): 5008-5016. And in: Na, Hanah, and Thomas S. Teets. "Highly luminescent cyclometalated iridium complexes generated by nucleophilic addition to coordinated isocyanides." Journal of the American Chemical Society 140, no. 20 (2018): 6353-6360. And in: Na, Hanah, Mina Song, and Thomas S. Teets. "Facile Synthesis of Luminescent Ir–Pt–Ir Trimetallic Complexes." Chemistry–A European Journal 25, no. 18 (2019): 4833-4842.