Within the past decade, tetraaryltetrabenzoporphyrins (TATBPs) have gained rising attention due to their potential in various fields of materials science and medicinal chemistry. However, this class of compounds still lacks in structural diversity, especially in the case of low-symmetrical compounds. Herein, mixed condensations were utilized to generate TATBPs with different substituents either in the meso-positions or the periphery of the macrocycle with total yields of 55–58%. The separation of crude mixtures was achieved by feasible chromatographic purification. The influence of symmetry on the electronic properties of TATBPs was studied by optical spectroscopy, electrochemistry, and X-ray diffraction.

Porphyrin‐based architectures have emerged as excellent candidates for artificial light‐harvesting antennae. Although tetrabenzoporphyrins (TBPs), the π‐extended “bigger brothers” of porphyrins, benefit from increased absorptivity in the near‐infrared (NIR), their utilization in light‐harvesting systems is still in its infancy. Within this work, we prepared two donor‐acceptor hetero dyads consisting of hexa‐peri‐hexabenzocoronenes (HBCs) to harvest high energetic near‐UV light, and a TBP core, which serves as visible to NIR light antenna and as subsequent energy sink of the conjugate. The HBCs are either attached to the meso‐position or via a maleimide‐bridge on the periphery of the macrocycle. Upon excitation of the HBC moieties, both dyads exhibit an efficient energy transfer to the TBP core. Furthermore, the TBP‐HBC dyads show superior light‐harvesting properties compared to the respective HBC‐porphyrin reference and the naturally occurring chlorophylls a/b.

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We will present our research towards tetraaryltetrabenzoporphyrins. This will include synthetic approaches to unsymmetrical derivatives and interactions with fullerenes. We report on the synthesis, characterization, and properties of some of these novel systems, including structures formed on surfaces.[1-4] References [1] M. Ruppel, D. Lungerich, S. Sturm, R. Lippert, F. Hampel, N. Jux, Chem. Eur. J. 2020, 26, 3287-3296. [2] M. Ruppel, L.-P. Gazetas, D. Lungerich, F. Hampel, N. Jux, J. Org. Chem. 2020, 85, 7781-7792. [3] M. Ruppel, L.-P. Gazetas, D. Lungerich, N. Jux, Eur. J. Org. Chem. 2020, 40, 6352-6360. [4] R. Adhikari, J. Kuliga, M. Ruppel, N. Jux, H. Marbach, H.-P. Steinrueck, J. Phys. Chem. C 2021, 125, 7204-7212. Figure 1