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 meta...

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Published inInorganic chemistry Vol. 63; no. 26; pp. 11944 - 11952
Main Authors Snyder, Graden, Abuhadba, Sara, Lin, Neo, Lee, Wei-Tsung, Mani, Tomoyasu, Esipova, Tatiana V.
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 01.07.2024
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Summary: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.
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ISSN:0020-1669
1520-510X
1520-510X
DOI:10.1021/acs.inorgchem.4c00055