Photophysical Properties of Fluorescent 2-(Phenylamino)-1,10-phenanthroline Derivatives†

Abstract

The present study details the experimental and theoretical characterization of the photophysical properties of 14 examples of 2-(phenylamino)-1,10-phenanthrolines (1). The absorption spectra of 1 are substituent-dependent but in a general manner present absorption bands at wavelengths of ~230; ~300; ~335 and a shoulder at ~380 nm. Electron-donating groups (EDG) and electron-withdrawing groups (EWG), respectively, result in bathochromic and hypsochromic shifts. Compounds 1 are highly luminescent, in contrast to phenanthroline, and emit in the region between 350 and 500 nm with substituent-dependent λ_max emission. The emission spectra show a redshift for EDG (4-OMe 62 nm; 4-Me 19 nm) and a blueshift for EWG (4-CN 41 nm; 4-CF₃ 38 nm) relative to the emission of the unsubstituted parent compound 1a. Plotting the ${\lambda }_{max}^{\text{EM}}$ against Hammett σ+ constants gave an excellent linear correlation demonstrating the electron-deficient nature of the excited state and how the substituents (de)stabilize S₁ . Theoretical calculations revealed a HOMO-LUMO π-π* electronic transition to S₁ which in combination with difference (S₁ -S₀ ) in electron density maps revealed charge-transfer character. Strongly electron-withdrawing substituents switch off the charge transfer to give rise to a local excitation.