Datasets presented for ' Photogeneration of Spin Quintet Triplet−Triplet Excitations in DNA-Assembled Pentacene Stacks' Figure 1d.dat was generated as described in the Supporting Informaton, Section D Figure 2a.dat was measured as described in the Supporting Informaton, Section A Figure 2b-e was measured as described in the Supporting Informaton, Section A Figure 2f.dat is the extracted SF rate constants, extracted as described in the Supporting Information, Section I. Figure 3 and 4 were measured and analysed as described in the Supporting Information, Sections A and K.