Thömmes Anna-Lena, Büttner Thomas, Morgenstern Bernd, Janka Oliver, Kickelbick Guido, Niebuur Bart-Jan, Kraus Tobias, Gallei Markus, Scheschkewitz David
Krupp-Chair for General and Inorganic Chemistry, Saarland University, 66123, Saarbrücken, Germany.
Inorganic Solid-State Chemistry, Saarland University, 66123, Saarbrücken, Germany.
Angew Chem Int Ed Engl. 2024 Dec 16;63(51):e202415103. doi: 10.1002/anie.202415103. Epub 2024 Nov 16.
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.
尽管含杂原子的共轭聚合物备受关注，但在共轭路径中含有较重p区元素的例子却很少。最近报道的重质非环二烯复分解反应（HADMET）使得合成含有Ge=Ge双键的聚合物成为可能，尽管该聚合物不溶且聚合度有限。通过引入长烷基链，我们现在得到了可溶的聚合物，根据扩散排序核磁共振光谱（DOSY）和动态光散射（DLS），其聚合度接近无穷大。紫外/可见光谱和核磁共振数据证实了在Ge=Ge双键之间的硅烯-亚苯基连接基上存在σ,π-共轭。有利的分子间分散相互作用导致形成梯状圆柱形聚集体，这通过X射线衍射（XRD）、小角X射线散射（SAXS）和DLS得到了证实。沉积薄膜的原子力显微镜（AFM）和透射电子显微镜（TEM）图像揭示了延伸聚合物束的层状有序排列。
