Abstract: | π‐Conjugated molecular cages are very challenging targets in structural organic chemistry, supramolecular chemistry, and materials science. The synthesis and physical characterizations are reported of the first three‐dimensionally π‐conjugated diradical molecular cage PTM‐C, in which two polychlorotriphenylmethyl (PTM) radicals are linked by three bis(3,6‐carbazolyl) bridges. This cage compound was synthesized mainly by intermolecular Yamamoto coupling followed by deprotonation and oxidation. It is stable and its structure was confirmed by X‐ray crystallographic analysis. The two carbon‐centered PTM radicals are weakly coupled through electronic interactions with the carbazole spacers, as revealed by optical, electronic, and magnetic measurements as well as theoretical calculations. |