Uncovering the substituted-position effect on excited-state evolution of benzophenone-phenothiazine dyads

Photofunctional materials based on donor-acceptor molecules have drawn intense attention due to their unique optical properties. Importantly, Systematic investigation of substitution effects on excited-state charge transfer dynamics of donor-acceptor molecules is a powerful approach for identifying application-relevant design principles. Here, by coupling phenothiazine (PTZ) at the ortho-, meta-, and para-positions of the benzene ring of benzophenone (BP), three regioisomeric BP-PTZ dyads were designed to understand the relationship between substituted positions and excited-state evolution channels. Ultrafast transient absorption is used to detect and trace the transient species and related evolution channels of BP-PTZ dyads at excited state. In a non-polar solvent, BP-o-PTZ undergoes the through-space charge transfer process to produce a singlet charge-transfer ((CT)-C-1) state, which subsequently proceeds the intersystem crossing process and transforms into a triplet charge-transfer ((CT)-C-3) state; BP-m-PTZ experiences intramolecular charge transfer (ICT) process to generate the (CT)-C-1 state, which subsequently transforms into the (CT)-C-3 state by the intersystem crossing (ISC) and finally converts into the local-excited triplet ((LE)-L-3) state; as for BP-p-PTZ, only (LE)-L-3 states can be detected after the ISC process from the (CT)-C-1 state. On the other hand, the twisted ICT states are generated via twisted motion between the donor and acceptor for all BP-PTZ dyads or planarization of the PTZ unit in high polar solvents. The excited-state theoretical calculations unveil that the features of ICT and intramolecular interaction between the three dyads play a decisive role in determining the through-bond charge transfer and through-space charge transfer processes. Also, these results demonstrate that the excited-state evolution channels of PTZ derivatives could be modified by tuning the substituted positions of the donor-acceptor dyads. This study provides a deep perspective for the substitute-position effect on donor-acceptor-type PTZ derivatives.