Electronic communication and negative binding cooperativity in diborylated bithiophenes

The bifunctional conjugated organoboranes Ar2B-bt-BAr2, which contain 2,2'- bithiophene (bt) linkers and different aryl substituents on boron (3: Ar = p-(BuC6H4)-Bu-t; 4: Ar = C6F5; 5: Ar = C6F5, Fc; Fc = ferrocenyl), have been synthesized. The electronic communication between the boron centers and cooperativity effects in the binding of pyridine have been investigated by a comprehensive study using X-ray crystallography, DFT calculations, cyclic voltammetry, H-1 and F-19 NMR, and UV visible absorption and emission spectroscopy. A comparison of the single-crystal X-ray structures of 4 and 4Py(2) revealed a strongly diminished bond alternation in the thiophene rings for 4, indicative of a high degree of electronic delocalization. DFT calculations are in good agreement with the structural features determined from the X-ray analysis and, consistent with the experimental absorption and emission data, predict a smaller HOMO-LUMO gap for green luminescent 4 in comparison to blue luminescent 3. The complexation of pyridine to the two boron centers was further investigated by H-1 and F-19 NMR for 4 and by H-1 NMR and UV-visible absorption spectroscopy for 3. We found that binding of the first pyridine molecule to one of the boryl groups significantly lowers the Lewis acidity of the other boryl group. For 3, the interaction parameter a, which provides a measure of communication between the boron sites, was determined to be a = 0.23 by UV-visible titration and 0.21 by H-1 NMR spectroscopy. Further enhanced electronic communication was observed for the more highly Lewis acidic fluorinated derivative 4, for which a = 0.025 according to 19F and H-1 NMR spectroscopy.