Intramolecular Electron Transfer through the 20-Position of a Chlorophyll a Derivative:  An Unexpectedly Efficient Conduit for Charge Transport

Suzuki cross-coupling reactions have afforded 20-phenyl-substituted Chlorophyll a derivatives (ZCPh) in good yields and significant quantities from readily available Chl a. A series of donor−acceptor dyads was synthesized in which naphthalene-1,8:4,5-bis(dicarboximide) or either of two perylene-3,4:9,10-bis(dicarboximide) electron acceptors is attached to the para position of the 20-phenyl group. Comparisons with the analogous dyads based on a zinc 5,10,15-tri(n-pentyl)-20-phenylporphyrin donor show that, for a given acceptor and solvent, the rates of photoinduced charge separation and recombination as well as the calculated electronic coupling matrix elements, V, for these reactions differ by less than a factor of 2. However, EPR and ENDOR spectroscopy corroborated by DFT calculations show that the highest occupied MO of ZCPh+• has little spin (charge) density at the 20-carbon atom, whereas Z3PnPh+• has significant spin (charge) density there, implying that V, and therefore the electron-transfer rates, should differ significantly for these two macrocyclic donors. DFT calculations on ZCPh+• and Z3PnPh+•, with two −0.5 charges located where the nearest carbonyl oxygen atoms of the acceptor would reside in the donor−acceptor dyads, show that the presence of the negative charges significantly shifts the charge density of both ZCPh+• and Z3PnPh+• from the macrocycle onto the phenyl rings. Thus, the presence of adjacent covalently linked radical anions at a fixed location relative to each of these radical cations results in nearly identical electronic coupling matrix elements for electron transfer and therefore very similar rates.