Polystannanes: Polymers of a Molecular, Jacketed Metal–Wire Structure

Abstract Organometallic polymers comprising a backbone of covalently connected metal atoms can be regarded as molecular metal wires surrounded by a jacket of organic matter. Such polymers are rare and their materials properties are largely unexplored. Here, we report on polystannanes, (SnR₂)_n, that is, polymers with a backbone of tin atoms, which are synthesized by dehydropolymerization of dialkylstannanes (H₂SnR₂) with the catalyst [RhCl(PPh₃)₃]. The polystannanes feature reversible phase transitions into liquid‐crystalline states, remarkably, even below room temperature, and, interestingly, oriented either parallel or perpendicular to external driving forces, depending on the length of the alkyl substituents.