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

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 Pd²⁺ and Pt²⁺ were synthesized and characterized. X-ray crystallography reveals that both complexes exhibit a zigzag geometry with square planar coordination of the central metal. The Pd²⁺ complex possesses a very weak fluorescence at 665 nm, while the Pt²⁺ 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.