Structural and Photophysical Characterization of All Five Constitutional Isomers of the Octaethyl‐β,β′‐dioxo‐bacterio‐ and ‐isobacteriochlorin Series

It is well‐known that treatment of β‐octaethylporphyrin with H2O2/conc. H2SO4 converts it to a β‐oxochlorin as well as all five constitutional isomers of the corresponding β,β’‐dioxo‐derivatives: two bacteriochlorin‐type isomers (β‐oxo groups at opposite pyrrolic building blocks) and three isobacteriochlorin‐type isomers (β‐oxo‐groups at adjacent pyrrolic building blocks). By virtue of the presence of the strongly electronically coupled β‐oxo auxochromes, none of the chromophores are archetypical chlorins, bacteriochlorins, or isobacteriochlorins. Here the authors present, inter alia, the single crystal X‐ray structures of all free‐base diketone isomers and a comparative description of their UV‐vis absorption spectra in neutral and acidic solutions, and fluorescence emission and singlet oxygen photosensitization properties, Magnetic Circular Dichroism (MCD) spectra, and singlet excited state lifetimes. DFT computations uncover underlying tautomeric equilibria and electronic interactions controlling their electronic properties, adding to the understanding of porphyrinoids carrying β‐oxo functionalities. This comparative study lays the basis for their further study and utilization. The single crystal structures, UV‐vis absorption spectra in neutral and acidic solutions, fluorescence emission properties, MCD spectra, and their singlet oxygen photosensitization properties of all octaethyl‐β,β’‐dioxo‐porphyrin isomers are presented. DFT Computations reveal the underlying tautomeric equilibria and the strong electronic interactions of the β‐oxo‐functionalities with the porphyrinic π‐system. This contribution adds to the understanding of porphyrinoids carrying the β‐oxo‐auxochrome and lays the foundation for their further utilization.