Synthesis, Redox Properties, and Electronic Coupling in the Diferrocene Aza-dipyrromethene and azaBODIPY Donor–Acceptor Dyad with Direct Ferrocene−α-Pyrrole Bond

3,3′-Diferrocenylazadipyrromethene (<b>3</b>) and corresponding difluoroboryl (azaBODIPY) complex (<b>4</b>) were synthesized in several steps from ferrocenecarbaldehyde, following the well-explored chalcone-type synthetic approach. The novel diiron complexes, in which ferrocene groups are directly connected to the α-pyrrolic positions were characterized by a variety of spectroscopic techniques, electrochemistry, spectroelectrochemistry, and X-ray crystallography, while their electronic structure, redox properties, and UV–vis spectra were correlated with the density functional theory (DFT) and time-dependent DFT calculations