Assembly Modulation of PDI Derivative as a Supramolecular Fluorescence Switching Probe for Detection of Cationic Surfactant and Metal Ions in Aqueous Media

Abstract

We report an amphiphilic perylene diimide (1), a bimolecular analog of L-3,4-dihydroxyphenylalanine (L-DOPA), as a reversible fluorescence switching probe for the detection and sensing of cationic surfactants and Fe3+/Cu2+ in an aqueous media respectively by means of host-guest interactions driven assembly and disassembly of 1. Photophysical studies of 1, going from dimethyl sulfoxide (DMSO) (State-I) to pure aqueous medium (State-II), suggested the formation of self-assembled aggregates by displaying very weak fluorescence emission along with red shifted broad absorption bands. Interestingly, the cationic surfactant cetyltrimethylammonium bromide (CTAB) could disassemble 1 in miceller conditions by restoring bright yellow fluorescence and vibronically well-defined (Franck-Condon progressions A(0-0)/A(0-1) approximate to 1.6) absorption bands of 1 over other neutral and anionic surfactants (State-III). Owing to the metal chelating nature of L-DOPA, 1 was able to sense Fe3+ and Cu2+ among a pool of other metal ions by means of fluorescence switching off state, attributed to metal interaction driven assembly of 1 (State-IV). Such metallosupramolecular assemblies were found to reverse back to the fluorescence switching on state using a metal ion chelator, diethylenetriaminepentaacetic acid (DTPA, State-III), further signifying the role of metal ions toward assembly of 1. Formation of assembly and disassembly could be visualized by the diminished and increased yellow emission under green laser light. Further, the assembly-disassembly modulation of 1 has been extensively characterized using infrared (IR), mass spectrometry, microscopy and dynamic light scattering (DLS) techniques. Therefore, modulation of the molecular self-assembly of PDI derivative 1 in aqueous media (assembled state, State-II) by means of host-guest interactions provided by micellar structures of CTAB (disassembled state, State-III), metal ion (Fe3+ and Cu2+) interactions (assembled state, State-IV) and metal ion sequestration using DTPA (disassembled state, State-III) is viewed as a supramolecular reversible fluorescence switching off-on probe for cationic surfactant CTAB and Fe3+/Cu2+.