Dual Chromophoric Meso‐Aryl BODIPYs with Aggregation Induced Red‐Emission Characteristics: Optical Properties and their Application in Fe³⁺ Detection

Abstract

Herein, we report the design of meso‐aryl BODIPYs as a structural motif for aggregation‐caused quenching (ACQ) to aggregation‐induced emission (AIE) transformation. A series of meso‐aryl BODIPY derivatives were synthesized, by systematically increasing the size of the chromophore at the meso‐position from phenyl to pyrene. The effect of various factors, such as the aryl ring size, solvents, viscosity, and metal cations, on the photophysical properties was analyzed. The emission properties are well correlated with the flexibility of the aromatic ring for free rotation around the Caryl−CBODIPY bond. Accordingly, meso‐phenanthrene BODIPY (PhB) has the highest emission characteristics. The emission property of less bulky aryl‐substituted BODIPYs increases by increasing the solvent viscosity. The interaction of Fe3+ ions with aryl‐BODIPYs provides a prominent photophysical response based on Lewis‐acid supported decomplexation of BF2 in aryl‐BODIPYs. The bichromophoric meso‐aryl BODIPYs exhibit notable intramolecular excitation energy transfer from the aromatic ring to the BODIPY core, which is higher in meso‐anthracene BODIPY(AB). Hence, decorating BODIPYs with polycyclic aromatic systems generates a twisted structure, which inhibits the π‐π stacking between the planar aromatic molecules. This can be proposed as an effective approach at the molecular level to convert planar aryl luminophores having ACQ to AIEgens. Besides, the meso‐pyrene BODIPY derivative shows excellent mechanofluorochromic behaviour.