Poly(thiophene iminoborane): A Poly(thiophene vinylene) (PTV) Analogue with a Fully BN-Doped Backbone

An unprecedented poly(thiophene iminoborane)-a boron-nitrogen analogue of the well-established conjugated organic polymer poly(thiophene vinylene)-is presented. The polymer synthesis is achieved by selective Si/B exchange polycondensation of a 2,5-diborylthiophene with a 2,5-diaminothiophene derivative. For the latter, a facile synthetic strategy is devised, which makes this versatile, strongly electron-releasing building block easily accessible. The novel polymer and a series of monodisperse thiophene iminoborane oligomers reveal systematic bathochromic shifts in their absorption with increasing chain length, and thus extended π-conjugation over the BN units along the backbone, which is further supported by TD-DFT calculations.