Conjugated Diphenylaniline-Azulene Co-Oligomers with Intense Absorption and Emission in the Visible Region.

New conjugated 2,6-diphenylaniline-azulene co-oligomers of linear and branched structure were synthesized by the interaction of borylazulenes with diphenylaniline bromides under Suzuki-Miyaura cross-coupling conditions. The obtained diphenylaniline-azulene co-oligomers intensively absorb and emit visible light (410-700 nm region); in particular, they exhibit strong emissions in the green, as well as orange, range, with maxima of 510/590 nm. It is shown that such properties appear as a result of the positive resonance exposure to aniline fragments significantly rearranging the electronic structure of azulene, in particular, the levels and energy gaps of frontal HOMO-LUMO orbitals.

Introduction of Electron Donor Groups into the Azulene Structure: The Appearance of Intense Absorption and Emission in the Visible Region.

In this work, through the Suzuki-Miyaura cross-coupling reaction with high yields, new π-conjugated azulene compounds containing diphenylaniline groups at positions 2 and 6 of azulene were synthesized. The obtained diphenylaniline-azulenes have intensely visible-light absorbing and emitting (in the wavelength range from 400 to 600 nm) properties. It has been shown that such unique optical properties, in particular fluorescent emission in the region of blue and green photoluminescence (λem at 495 and 525 nm), which were absent in the original azulene, are the result of the electron donor effect of diphenylaniline groups, which significantly changes the electronic structure of azulene and leads to the allowed HOMO → LUMO electron transition.