Dehydrocoupling and Silazane Cleavage Routes to Organic–Inorganic Hybrid Polymers with NBN Units in the Main Chain

Despite the great potential of both π-conjugated organoboron polymers and BN-doped polycyclic aromatic hydrocarbons in organic optoelectronics, our knowledge of conjugated polymers with B-N bonds in their main chain is currently scarce. Herein, the first examples of a new class of organic-inorganic hybrid polymers are presented, which consist of alternating NBN and para-phenylene units. Polycondensation with B-N bond formation provides facile access to soluble materials under mild conditions. The photophysical data for the polymer and molecular model systems of different chain lengths reveal a low extent of π-conjugation across the NBN units, which is supported by DFT calculations. The applicability of the new polymers as macromolecular polyligands is demonstrated by a cross-linking reaction with Zr(IV) .