| Summary: | A spirogermabifluorene that bears sterically demanding 3,3′,5,5′-tetra(<i>t</i>-butyl)-2,2′-biphenylene groups (<b>1</b>) was obtained from the reaction of in-situ-generated 2,2′-dilithiobiphenylene with GeCl<sub>2</sub>·(dioxane). The solid-state structure and the redox behavior of <b>1</b> were examined by single-crystal X-ray diffraction analysis and electrochemical measurements, respectively. The sterically hindered biphenyl ligands endow <b>1</b> with high redox stability and increased electron affinity. The experimental observations were corroborated by theoretical DFT calculations.
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