Connectivity Effect on Electronic Properties of Azulene-Tetraazapyrene Triads

Azulene-based chromophores are of growing interest due to their unique electronic structures and potential applications as pH-responsive optical materials. In this study, a series of azulene-1,3,6,8-tetraazapyrene (TAP) triads were successfully synthesized and characterized to systematically explore how connectivity between the TAP and azulene units influences their optical and redox properties. UV-Vis absorption spectroscopy and cyclic voltammetry measurements clearly show that the electronic properties depend heavily on the connectivity pattern, as the effective π-conjugation and molecular planarity vary considerably in triads. Remarkably, triads A₂₂ and A₂₆, in which the TAP core is directly connected through the electron-rich five-membered ring, exhibit enhanced π-conjugation and pronounced color changes upon protonation. In contrast, A₆₆, linked via the electron-deficient seven-membered ring, reveals weaker π-conjugation and less pronounced pH-responsiveness. These experimental findings are further supported by DFT calculations. This comprehensive structure-property relationship study provides valuable insights for the rational design of advanced optoelectronic and stimuli-responsive materials.