Electron Spin Dynamics of the Intersystem Crossing in Aminoanthraquinone Derivatives: The Spectral Telltale of Short Triplet Excited States

TL;DR

This study investigates the ultrafast intersystem crossing and unusually short triplet state lifetimes in aminoanthraquinone derivatives using femtosecond spectroscopy and TREPR, revealing insights into their excited state dynamics and electron spin polarization.

Contribution

It provides new experimental and computational insights into the spin dynamics and short-lived triplet states of aminoanthraquinone derivatives, highlighting the role of electron-vibrational coupling.

Findings

Intersystem crossing occurs within 190-320 ps.

Triplet state lifetimes are exceptionally short (2.1-5.4 microseconds).

Spectral simulations and Herzberg-Teller effects explain the observed spin polarization inversion.

Abstract

Herein we studied the excited state dynamics of two bis-amino substituted anthraquinone (AQ) derivatives. Femtosecond transient absorption spectra show that intersystem crossing (ISC) takes place in 190-320 ps, and nanosecond transient absorption spectra demonstrated unusually short triplet state lifetime (2.1-5.4 us) for the two AQ derivatives at room temperature. Pulsed laser excited time-resolved electron paramagnetic resonance (TREPR) spectra shows an inversion of the electron spin polarization (ESP) phase pattern of the triplet state at longer delay time. Spectral simulations show that the faster decay of the Ty sublevel (x = 15.0 us, y = 1.50 us, z = 15.0 us) rationalizes the short T1 state lifetime and the ESP inversion. Computations taking into account the electron-vibrational coupling, i.e., the Herzberg-Teller effect, successfully rationalize the TREPR experimental observations.