Conjugated polymers have found widespread applications in thin film electronic devices. Among a plethora of examples, low bandgap poly(thienylene vinylene) (PTV) derivatives have attracted increasing attention due to high charge mobilities, environmental and thermal stability, and recently discovered singlet fission processes. However, these PTVs possess extremely short exciton lifetimes that significantly limit their applications in organic optoelectronic devices. Thus, structural modifications and a better understanding on structure-property relationships are necessary, which has been explored to a very limited extent mainly due to the limitations in conventional synthetic methodologies. Here, we report two distinctive methods for modifying PTV structures and properties. First, we synthesized poly(3-decylselenylene vinylene) (P3DSV) homopolymers and poly(3-decylselenylene vinylene)-co-poly(3-decylthienylene vinylene) (P3DSV-co-P3DTV) copolymers through acyclic diene metathesis (ADMET) polymerization techniques.1 By replacing sulfur atoms with selenium, P3DSV was found to possess reduced crystallinity and a smaller bandgap of ca. 1.6 eV, and P3DSV-co-P3DTV shows physical/electronic properties between those of the corresponding homopolymers. Secondly, we successfully prepared a series of novel PTV derivatives functionalized with F, Cl, Br and I atoms at the 4-positions of thiophene rings through ADMET. Such halogenation not only displays capabilities of fine-tuning polymer properties but also provides opportunities for further functionalization through cross-coupling reactions. Our methodologies provide new ways to systematically study the structure-property relationships of low bandgap poly(chalcogenolene vinylene)s, which has been rarely explored previously. 1 Zhang, Z. and Qin, Y. ACS Macro Lett. 2015, 4, 679.

Novel poly(chalcogenylene vinylene)s with systematically tuable physical and electronic properties through acyclic diene metathesis (ADMET)

251st National Meeting (2016)

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