The Degree of Charge Transfer in Ground and Charge-Separated States Revealed by Ultrafast Visible Pump/Mid-IR Probe Spectroscopy

Abstract

We demonstrate a new femtosecond visible pump/mid-IR probe spectroscopic approach to assess directly the ground- and excited-state degrees of charge transfer (CT) in donor-spacer-acceptor (D-Sp-A) structures. Two classes of (porphinato)zinc(II) (PZn)-based D-Sp-A compounds with either quinonyl (Q) or N-(N'-octyl)pyromellitic diimide (PI) electron acceptors were interrogated. Carbonyl antisymmetric stretching mode frequency domain transient-IR spectra of these species were recorded and analyzed for the Q/PI moieties. These data show that the acceptor mode frequency shift, DeltanuA, determined by this method provides a more accurate measure of the degree of CT in ground and charge-separated states relative to other techniques which rely on the ground-state frequency shift alone. This approach enables determination of new experimental benchmarks to test the power of complimentary computational methods and provides a means to probe the degree of CT in transitions that either overlap strongly with other bands or possess low oscillator strength.