Ultrafast conformational dynamics of electron transfer in ExBox ⁴⁺⊂Perylene

Abstract

Multielectron acceptors are essential components for artificial photosynthetic systems that must deliver multiple electrons to catalysts for solar fuels applications. The recently developed boxlike cyclophane incorporating two extended viologen units joined end-to-end by two p-phenylene linkers - namely, ExBox4+ - has a potential to be integrated into light-driven systems on account of its ability to complex with π-electron-rich guests such as perylene, which has been utilized to great extent in many light-harvesting applications. Photodriven electron transfer to ExBox4+ has not previously been investigated, however, and so its properties, following photoreduction, are largely unknown. Here, we investigate the structure and energetics of the various accessible oxidation states of ExBox4+ using a combination of spectroscopy and computation. In particular, we examine photoinitiated electron transfer from perylene bound within ExBox4+ (ExBox4+⊂perylene) using visible and near-infrared femtosecond transient absorption (fsTA) spectroscopy. The structure and conformational relaxation dynamics of ExBox3+⊂ perylene+ are observed with femtosecond stimulated Raman spectroscopy (FSRS). From the fsTA and FSRS spectra, we observe that the central p-phenylene spacer in one of the extended viologen units on one side of the cyclophane becomes more coplanar with its neighboring pyridinium units over the first ∼5 ps after photoreduction. When the steady-state structure of chemically generated ExBox2+ is investigated using Raman spectroscopy, it is found to have the central p-phenylene rings in both of its extended viologen units rotated to be more coplanar with their neighboring pyridinium units, further underscoring the importance of this subunit in the stabilization of the reduced states of ExBox4+. © 2013 American Chemical Society.