Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurements were used to infer the HOMO/LUMO levels of TPPQ, 4DMAC-TPPQ, and 4PXZ-TPPQ in DCM. The voltammograms are shown in Figure and the data are summarized in Table . As expected, there is no observable oxidation wave for TPPQ, while there are two 1-electron reversible reduction waves at Ered1 = -1.00 V and Ered2 = -1.49 V vs SCE in DCM, in line with the literature-reported electrochemistry. The corresponding orbital energies are LUMO = -3.34 eV and LUMO+1 = -2.85 eV. 4DMAC-TPPQ possesses a quasi-reversible oxidation wave at Eox at 1.00 V vs SCE, which is assigned to the oxidation of the DMAC donor moieties as this value aligns with the previously reported Eox of 1.04 V for the DMAC-containing compound DMAC- a-DK. The reversible oxidation wave of 4PXZ-TPPQ is shifted cathodically at 0.79 V vs SCE and is attributed to the oxidation of the PXZ donor moieties; indeed, the Eox of 4PXZ-TPPQ is similar to that of a related PXZ-containing compound, PXZPDO (Eox = 0.83 V). The HOMO levels thus are -5. The estimated HOMO level of TPPQ is inferred to be -6.12 eV from the difference between LUMO level and the optical gap (DEg = 2.78 eV) of TPPQ (Table ). The HOMO-LUMO energy gap of TPPQ (2.78 eV) is much larger than that of 4DMAC-TPPQ (1.89 eV) and 4PXZ-TPPQ (1.69 eV).