Synthesis and optical and electrochemical properties of julolidine-structured pyrido[3,4-b]indole dye

Abstract

The julolidine-structured pyrido[3,4-b]indole dye ET-1 has been newly designed and developed as a small D–A fluorescent dye. ET-1 showed bathochromic shifts of the fluorescence band upon changing from aprotic solvents to protic solvents, as well as positive fluorescence solvatochromism. Moreover, it was found that ET-1 can form a 1 : 1 Py(N)–B complex with boron trifluoride and a hydrogen-bonded proton transfer (Py(N)–H) complex with trifluoroacetic acid, which exhibit photoabsorption and fluorescence bands at a longer wavelength region than the pristine ET-1. Based on optical (photoabsorption and fluorescence spectroscopy) and electrochemical (cyclic voltammetry) measurements, Lippert–Mataga plots, ¹H NMR spectral measurement and density functional theory (DFT) calculation, this work indicated that the Py(N)–B complex or the Py(N)–H complex is effectively formed and stable in solution. This is due to the strong Py(N)–B interaction or Py(N)–hydrogen-bond, which can be attributed to the enhanced basicity or the accumulated electron density on the nitrogen atom of the pyridine ring caused by the introduction of a julolidine (quinolizidine) moiety as a strong electron-donating group. We propose that the D–A-type dye ET-1 based on the julolidine-structured pyrido[3,4-b]indole possesses the ability to act as a calorimetric and fluorescent sensor for Brønsted and Lewis acids.