Cascade Synthesis of Benzotriazulene with Three Embedded Azulene Units and Large Stokes Shifts

Abstract

We report here the one-pot synthesis of benzo[1,2-a : 3,4-a' : 5,6-a'']triazulene (BTA), wherein three azulene units are embedded through a tandem reaction comprising two steps, Suzuki coupling and Knoevenagel condensation, between a readily available triborylated truxene precursor and 8-bromo-1-naphthaldehyde. Its nitration leads to a regioselective trinitrated product, namely, BTA-NO₂ . Single-crystal X-ray crystallography revealed that the superstructure of BTA consists of a dimer stacked by two enantiomeric helicene conformers, while that of BTA-NO₂ consists of an unprecedented π-tetramer stacked from two enantiomeric dimers, that is, four distinct helicene conformers. Both compounds show excellent stability and fluorescence with large Stokes shifts of up to 5100 cm^-1 . In addition, BTA-NO₂ exhibits a unique solvatochromic effect in different solvents and hydrogen-bonding-induced emission transfer in different ratios of THF/H₂ O solutions.

Keywords: Annulation; Azulene; Polycyclic Aromatic Hydrocarbons; Structure Elucidation.