Fine tuning of the photophysical properties of cofacial diporphyrins via the use of different spacers

The crystal and molecular structures of two unmetallated diporphyrin species using the biphenylene and dibenzofuran spacers, H4(DPB) and H4(DPO), respectively (DPB 4 − =1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene; DPO 4 − =4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzofuran), are reported. These data are compared to their literature metallated analogs, stressing on the properties related to the flexibility of the ligands, ··· and M···M interactions. In addition, the lowest energy fluorescence properties of these non-phosphorescent diporphyrin compounds as well as three other related species, H4(DPA), H4(DPX), and H4(DPS) (DPA 4 − …