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Pd and Pt Complexes of Benzo-Fused Dipyrrins: Synthesis, Structure, Electrochemical, and Optical Properties.

Graden SnyderSara AbuhadbaNeo LinWei Tsung LeeTomoyasu ManiTatiana V Esipova
Published in: Inorganic chemistry (2024)
Benzo-fused dipyrrins are π-extended analogs of conventional dipyrrins, which exhibit bathochromically shifted absorption and possess the synthetic capability to bind various metal ions. We aimed to investigate the synthetic potential of benzo-fused dipyrrins in the complexation with transition metals. Two new complexes with Pd 2+ and Pt 2+ were synthesized and characterized. X-ray crystallography reveals that both complexes exhibit a zigzag geometry with square planar coordination of the central metal. The Pd 2+ complex possesses a very weak fluorescence at 665 nm, while the Pt 2+ complex is completely nonemissive. Transient absorption spectroscopy confirmed triplet excited state formation for both complexes; however, they are short-lived and no phosphorescence was observed even at 77K. DFT calculations support the experimental observation, revealing the existence of the low-lying ligand-metal charge-transfer (LMCT) triplet state acting as an energy sink.
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