Tetragermatetrathiacirculene has successfully been synthesized from tetraiodotetrathienylene through palladium-catalyzed germylation and rhodium-catalyzed intramolecular dehydrogenative cyclization. A single-crystal X-ray diffraction analysis elucidated that tetragermatetrathiacirculene has a highly symmetric, planar, and rigid structure. DFT calculations suggested that LUMO of tetragermatetrathiacirculene is stabilized due to σâÏ€∗ interactions between σ∗ orbitals of the Ge-C bonds and Ï€∗ orbitals of the thiophene rings. The excited dynamics of tetragermatetrathiacirculene have also been found to be significantly affected by the heavy-atom effect of the germanium atom.
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