Journal of Physical Chemistry A, Vol.119, No.22, 5618-5625, 2015
Ultrafast Intramolecular Electron and Proton Transfer in Bis(imino)isoindole Derivatives
Concerted motion of:electrons and protons in the excited state is pertinent to a wide range of Chemical phenomena, including those relevant for stilar-to-fuel tight harvesting. the excited state dynamics small proton-bearing molecules are expected to serve as models for better,understanding such phenomena. In particular, for designing the next generation,of multielectron and multiproton redox catalysts, understanding the dynamics of More, than one proton in the excited state is important. Toward this goal; We have measured the ultrafast dynamics of intramolecular excited state proton :transfer in a recently synthesized dye with two equivalent :transferable protons. We have used a visible ultrafast pump to initiate the proton transfer in the excited state, and have probed the transient absorption of the molecule over a Wide bandwidth in the visible range. The Measurement shows that the signal which is characteristic of proton transfer emerges Within similar to 710 fs. To identify Whether both protons were transferred in the excited state, we have Measured the ultrafast dynamics of a related derivative, where only a single proton was available for transfer. The measured proton transfer tine in that molecule was similar to 427 fs. The observed dynamics in both cases were reasonably fit with single exponentials. Supported :by the ultrafast, observations, steady-state fluorescence, and preliminary computations of the relaxed excited states, we argue that the doubly protonated derivative most likely transfers only one of its two protons in the excited state. We have performed calculations of the frontier molecular orbitals' in the Franck-Condon region. The-calculations show that in both derivatives, the excitation is primarily from the HOMO to LUMO causing a large rearrangement of the electronic charge density immediately after photoexcitation. In particular, charge density is shifted away from the phenolic protons and toward the proton acceptor nitrogens. The proton transfer, is hypothesized to occur both due to enhanced acidity of the phenolic proton and enhanced basicity of the nitrogen in the excited state. We hope this study can provide insight for better understanding of the general-class of excited state concerted electron-proton dynamics.