Local environment inside a novel aromatic micelle investigated by steady-state and femtosecond fluorescence spectroscopy of an encapsulated solvatochromic probe

Abstract

The local environment within a recently developed anthracene-shelled micelle (ASM), which is a micelle-like nanocapsule composed of anthracene-embedded amphiphiles, was investigated by steady-state and time-resolved spectroscopy of an encapsulated solvatochromic fluorescent probe molecule, coumarin 153 (C153). The absorption maximum of encapsulated C153 (452 nm) is more red-shifted than that of free C153 in water, indicating a highly polar environment inside the micelle. Despite this, the fluorescence Stokes shift of encapsulated C153 (∼3700 cm⁻¹) is substantially smaller than that of free C153 in water. Femtosecond time-resolved broadband fluorescence measurements further showed that the dynamic Stokes shift is completed within 1 ps, revealing that the reorganization of the micelle interior following photoexcitation of the C153 probe is characterized by a sub-picosecond, limited-amplitude response. The femtosecond fluorescence anisotropy data showed that the orientational diffusion of the host–guest complex is slower (860 ps) than that of the empty micelle (510 ps), suggesting that the micelle structure is flexible enough to expand when the guest molecule is accommodated and that the micelle rotates with the encapsulated guest molecule. This softness of the micelles further allows some of them to simultaneously encapsulate two C153 molecules, as evidenced by the appearance of blue-shifted, H-dimer-like absorption and fluorescence bands. Based on these steady-state and femtosecond time-resolved spectroscopic data, we discuss the electronic state of C153 and micelle structure as well as the host–guest interaction in this novel flexible synthetic nanocapsule.