Electron Transfer and Multi- Electron Accumulation in ExBox4+**

Molecules capable of accepting and storing multiple electrons are crucial components of artificial photosynthetic systems designed to drive catalysts, such as those used to reduce protons to hydrogen. ExBox(4+), a boxlike cyclophane comprising two -electron-poor extended viologen units tethered at both ends by two p-xylylene linkers, has been shown previously to accept an electron through space from a photoexcited guest. Herein is an investigation of an alternate, through-bond intramolecular electron-transfer pathway involving ExBox(4+) using a combination of transient absorption and femtosecond stimulated Raman spectroscopy (FSRS). Upon photoexcitation of ExBox(4+), an electron is transferred from one of the p-xylylene linkers to one of the extended viologen units in ca. 240ps and recombines in ca. 4ns. A crystal structure of the doubly reduced species ExBox(2+) was obtained.