Highly Tin‐Selective Stille Coupling: Synthesis of a Polymer Containing a Stannole in the Main Chain

Abstract

The incorporation of heavier Group 14 element heteroles into semiconducting polymers leads to unusual optoelectronic properties. However, polymers containing stannoles have not been accessible to date. We report a synthetic route to a well-defined, stannole-containing polymer, the first example of this class of π-conjugated polymers. This route was made possible by developing difunctionalized stannole monomers and highly tin-selective Stille coupling reactions that leave the tin in the stannole untouched. Compared to poly(3-n-hexylthiophene), the resulting polymer displays a remarkable bathochromic shift in its absorption.

Marriage of heavy main group elements with π-conjugated materials for optoelectronic applications

“…Please do not adjust margins Please do not adjust margins In 2014, Staubitz and coworkers developed a selective Stille coupling procedure that enabled the preparation of the first high molecular weight polystannole. 122 The authors initially In a recent paper by the Jäkle group, the planar chiral dimethyl tin-bridged biferrocene (131; Fig. 12) was prepared and that step-wise oxidation of the two Fe(II) centers to Fe(III) sites was possible.…”

“…The UV-vis spectrum of 130 in chloroform showed a broad absorption peak at 536 nm, which was significantly red-shifted in comparison to the monomer 129 (λ max = 441 nm). In addition the presence of stannole repeat units led to significant red-shifting of the absorption in relation to regioregular poly(3-hexylthiophene) (λ max = 450 nm) 122. Spin-coated films of 130 displayed a further red-shift in λ max.…”

Funktionelle polymere Materialien auf der Basis von Hauptgruppen‐Elementen

“…Zirconacyclen aus der reduktiven Cyclisierung von Dialkinen mit "Cp 2 Zr" wurden fürd iese Zwecke breit eingesetzt. [156] Der Ansatz auf Basis metallacyclischer Vorstufen wurde von Tomita und Zhou für bequeme Polymermodifikationsprozesse erweitert (86; Schema 9c). Ein repräsentatives Beispiel ist die Synthese von Poly(2,5silol) ( [155] Staubitz et al berichteten über die Herstellung von Stannol-Thiophen-Copolymeren mittels Stille-Kupplungspolymerisation( 85;S chema 9b).…”

Rosenthal’s Zirconocene

“…1 Therefore, this complex is treated in situ with pyridine, giving high yields of 2 (up to 85%). 3 This mild reactivity not only allows the reductive coupling of bromide-functionalized alkynes, 6 but also of iodide-substituted species. 3 In the latter example, the zirconacyclopentadiene that was obtained was transformed in situ into a stannole by a Zr-Sn exchange, carried out in toluene, in an overall yield of 81%.…”