Next, we turn our attention to DFT-based electronic structure calculations of the ground state of molecules built using the fragments shown in Figure . Regarding side chain substitutions, we corroborate the results shown in Figure , where excessive electronic conjugation leads to an excitation localized on the side chain with no participation from the backbone π-orbital that transforms to the σ-bond formed during the photoactivated electrocyclization. This can be readily seen in the HOMO and LUMO spatial distributions along the X-CP-X series shown in Figure , with X = T, TPh, TNaph and TAnt groups.