Synthesis and solvatochromism of a NIR II emissive amphiphilic aza-BODIPY dye and its application as a colorimetric and fluorometric probe in sequential detection of Cu2+ and PO43−

Abstract

The amphiphilic aza-BODIPY 1 bearing two N,N-dialkyl-amino groups at the para-positions of the 1,7-phenyl and two amino groups modified by a pair of hydrophilic chains at the para-positions at the 3,5-phenyl of the boron-azadipyrromethene core was synthesized and characterized. UV/Vis/NIR spectroscopic measurements indicated that the S₀–S₁ absorption band 1 reached up to 900 nm while its emission band reached up to 1200 nm. The solvatochromic properties of 1 was investigated by absorption and fluorescence spectroscopy and further analysed by the Lippert–Mataga equation. The results suggested a strong intramolecular charge transfer (ICT) effect of dye 1 stemming from the electron-donating amino groups, which was further confirmed by DFT calculation studies. Such ICT could be disrupted upon addition of Cu²⁺ owing to the metal–ligand interaction between Cu²⁺ and the amino moieties, leading to a hypsochromic shift of the absorption band concomitant with a significant decrease in the fluorescence intensity of 1. Moreover, the spectroscopic properties of 1 were recovered upon subsequent addition of PO₄³⁻ in [1 + Cu²⁺] solution. Based on these observations, the dye 1 was applied successfully as a NIR colorimetric and fluorometric “turn-off” probe for selective detection of Cu²⁺ (LOD = 2.1 μM). Subsequent fluorometric “turn-on” detection of PO₄³⁻ by [1 + Cu²⁺] (LOD = 3.0 μM) was accomplished in further studies.