1,3‐Bis(tetrylene)s: Emerging Platforms for Functional Main‐Group Molecules

Main‐group chemistry has undergone a resurgence as chemists seek reactivity patterns that do not rely on transition metals. Among low‐valent main‐group compounds, tetrylenes (R 2 E:, E = Si, Ge, Sn, Pb) occupy a central position because their ambiphilic electronic structures enable diverse bond activation and coordination chemistry. Although adjacent low‐valent Group 14 systems, including 1,2‐bis(tetrylene)s, ditetrynes, and related heavier alkyne‐type compounds, have been widely investigated as cooperative platforms, 1,3‐bis(tetrylene)s remain comparatively underexplored. In this review, we summarize recent developments in 1,3‐bis(tetrylene) chemistry, with emphasis on synthesis, structure, electronic properties, and reactivity. The discussion is organized according to the identity of the bridging atom, covering systems bridged by pnictogen, chalcogen, and tetrel (Group 14) elements. By comparing these bridge motifs, we highlight how electronic stabilization, steric protection, and geometric constraint govern the balance between stability and reactivity. Finally, we discuss future opportunities for using 1,3‐bis(tetrylene)s as cooperative main‐group platforms for bond activation, ligand design, catalysis, and the construction of heavy‐element π systems.