Hydrogen bond configuration and protonation of ground and lowest excited triplet states of 4‑amino‑4'‑nitrobiphenyl based on nanosecond transient absorption spectroscopy.

Abstract

Intramolecular charge transfer (ICT) is an important photochemical process. In contrast to those in singlet manifold, triplet ICT states were less studied. In this paper, the lowest excited triplet state (T1) of 4‑amino‑4'‑nitrobiphenyl (NH2-Bp-NO2) was recorded with nanosecond transient absorption spectroscopy in acidic acetonitrile and alcoholic solutions. By employing the Kamlet-Taft model to analyze the correlation between absorption maxima and alcohol solvent properties including polarity/polarizability, abilities of hydrogen bond donating and hydrogen bond accepting, hydrogen bond configuration in the ground state (S0) and T1 was resolved. The results suggest that the hydrogen bond between amino H and alcohol is dominant in S0, while in T1, hydrogen bonds between amino H and alcohol, between nitro O and alcohol have comparable contribution. By examination of the 1‑naphthol quench effect on T1, the hydrogen bond between nitro O and alcohol was confirmed present. Theoretical calculation results on the model of NH2-Bp-NO2-(MeOH)3 also indicate that hydrogen bonds between amino H and alcohol, between nitro O and alcohol are both much stronger in T1 than in S0. In acidic acetonitrile solution, in S0 of NH2-Bp-NO2 the amino group is protonated with pKa of 4.5, meanwhile in T1 the nitro group is much easier to be protonated than in S0. Its conjugated acid was measured to have a pKa of 3.1.