Observation of the Strong Electronic Coupling in Near-Infrared-Absorbing Tetraferrocene aza-Dipyrromethene and aza-BODIPY with Direct Ferrocene−α- and Ferrocene−β-Pyrrole Bonds: Toward Molecular Machinery with Four-Bit Information Storage Capacity

The
1,3,7,9-tetraferrocenylazadipyrromethene (3) and the
corresponding 1,3,5,7-tetraferrocene aza-BODIPY (4) were
prepared via three and four synthetic steps, respectively, starting
from ferrocenecarbaldehyde using the chalcone-type synthetic methodology.
The novel tetra-iron compounds have ferrocene groups directly attached
to both the α- and the β-pyrrolic positions, and the shortest
Fe–Fe distance determined by X-ray crystallography for 3 was found to be ∼6.98 Å. These new compounds
were characterized by UV–vis, nuclear magnetic resonance, and
high-resolution electrospray ionization mass spectrometry methods,
while metal–metal couplings in these systems were probed by
electro- and spectroelectrochemistry, chemical oxidations, and Mössbauer
spectroscopy. Electrochemical data are suggestive of the well-separated
stepwise oxidations of all four ferrocene groups in 3 and 4, while spectroelectrochemical and chemical oxidation
experiments allowed for characterization of the mixed-valence forms
in the target compounds. Intervalence charge-transfer band analyses
indicate that the mixed-valence [3]+ and [4]+ complexes belong to the weakly coupled class
II systems in the Robin–Day classification. This interpretation
was further supported by Mössbauer spectroscopy in which two
individual doublets for Fe­(II) and Fe­(III) centers were observed in
room-temperature experiments for the mixed-valence [3]n+ and [4]n+ species (n = 1–3). The
electronic structure, redox properties, and UV–vis spectra
of new systems were correlated with Density Functional Theory (DFT)
and time-dependent DFT calculations (TDDFT), which are suggestive
of a ferrocene-centered highest occupied molecular orbital and chromophore-centered
lowest unoccupied molecular orbital in 3 and 4 as well as predominant spin localization at the ferrocene fragment
attached to the α-pyrrolic positions in [3]+ and [4]+.