Near‐Infinite‐Chain Polymers with Ge=Ge Double Bonds.

Despite considerable interest in heteroatom‐containing conjugated polymers, there are only few examples with heavier p‐block elements in the conjugation path. The recently reported heavier acyclic diene metathesis (HADMET) allowed for the synthesis of a polymer containing Ge=Ge double bonds—albeit insoluble and with limited degree of polymerization. By incorporation of long alkyl chains, we now obtained soluble representatives, which exhibit degrees of polymerization near infinity according to diffusion‐ordered NMR spectroscopy (DOSY) and dynamic light scattering (DLS). UV/Vis and NMR data confirm the presence of σ,π‐conjugation across the silylene‐phenylene linkers between the Ge=Ge double bonds. Favorable intermolecular dispersion interactions lead to ladder‐like cylindrical assemblies as confirmed by X‐ray diffraction (XRD), small angle X‐ray scattering (SAXS) and DLS. AFM and TEM images of deposited thin films reveal lamellar ordering of extended polymer bundles. [ABSTRACT FROM AUTHOR]