# Connectivity Effect on Electronic Properties of Azulene–Tetraazapyrene Triads

## TL;DR

This study explores how the connectivity between azulene and TAP units affects the electronic and optical properties of triads, revealing how structure influences function in potential optoelectronic materials.

## Contribution

The paper systematically demonstrates how connectivity patterns affect π-conjugation and pH-responsiveness in azulene–TAP triads.

## Key findings

- Triads connected via the five-membered ring show enhanced π-conjugation and pronounced color changes upon protonation.
- Triads linked via the seven-membered ring exhibit weaker π-conjugation and reduced pH-responsiveness.
- DFT calculations support the experimental findings on structure–property relationships.

## Abstract

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.