Modulating the intersystem crossing mechanism of anthracene carboxyimide-based photosensitizers <i>via</i> structural adjustments and application as a potent photodynamic therapeutic reagent

Abstract

Herein, a series of compact anthracene carboxyimide (ACI) based donor-acceptor dyads were prepared by substituting bulky aryl moieties with various electron-donating ability to study the triplet-excited state properties. The ISC mechanism and triplet yield of the dyads were successfully tuned <i>via</i> structural manipulation. Efficient ISC (<i>Φ</i>_Δ ≈ 99%) and long-lived triplet state (<i>τ</i>_T ≈ 122 μs) was observed for the orthogonal anthracene-labeled ACI derivative compared to the Ph-ACI and NP-ACI dyads, which showed fast triplet state decay (<i>τ</i>_T ≈ 7.7 μs). Femtosecond transient absorption study demonstrated the ultrafast charge separation (CS) and efficient charge recombination (CR) in the orthogonal dyads and ISC occurring <i>via</i> spin-orbit charge transfer (SOCT) mechanism (AN-ACI: <i>τ</i>_CS = 355 fs, <i>τ</i>_CR = 2.41 ns; PY-ACI: <i>τ</i>_CS = 321 fs, <i>τ</i>_CR = 1.61 ns), while in Ph-ACI and NP-ACI dyads triplet populate following the normal ISC channel (nπ* → ππ* transition), no CS was observed. We found that the attachment of suitable aryl donor moiety (AN- or PY-) to the ACI core can ensure the insertion of the intermediate triplet state, resulting in a small energy gap among charge separated state (CSS) and triplet state, which leads to efficient ISC in these derivatives. The SOCT-ISC-based AN-ACI dyad was confirmed to be a potent photodynamic therapeutic reagent; an ultra-low IC₅₀ value (0.27 nM) that was nearly 214 times lower than that of the commercial Rose Bengal photosensitizer (57.8 nM) was observed.