and tCzBT2B which are both -5.43 eV. As the HOMO value of DtBuCzB is -5.26 eV in DCM, an analysis of the relative HOMO energies indicates that the substitution of the benzothienocarbazole moieties lead to a modest stabilization of the HOMO. The CVs of tDPABT1B, and tDPABT2B show irreversible reduction waves, with Ered (vs. SCE) of -1.81 and -1.79 V (from the DPV peaks). By contrast, the CV traces of tCzBT1B, and tCzBT2B show pseudo-reversible reduction waves, with Ered (vs. SCE) of -1.53 and -1.54 V (from the DPV peaks). These are anodically shifted compared to that of DtBuCzB (Ered = -1.70 in DCM). The corresponding LUMO energies for tCzBT1B, and tCzBT2B are -2.82 and -2.81 eV, respectively, which are stabilized by ca. 0.2 eV compared to that of DtBuCzB (-2.62 eV in DCM). Notably, the LUMO energies of tDPABT1B (-2.54 eV) and tDPABT2B (-2.56 eV) are moderately destabilized compared to tCzBT1B and tCzBT2B due to the decreased conjugation from the diphenyl amine moieties, which consequently leads to larger ΔEHOMO-LUMO of 2.77 and 2.78 eV, respectively, compared to 2.61 and 2.62 eV for tCzBT1B and tCzBT2B, respectively. The HOMO/LUMO energies of tCzBT1B (-5.43/-2.82 eV), and tCzBT2B (-5.43/-2.81 eV) are also close to its reported isomer BTC-BNCz (-5.37/-2.85 eV, measured in DCM). The trends in the orbital energies align well with the DFT calculations -5.19/-1.49 eV, -5.19/-1.50 eV, -5.40/-1.79 eV and -5.41/-1.79 eV for tDPABT1B, tDPABT2B, tCzBT1B and tCzBT2B, respectively (Figure ).