Dominik Lungerich

The underrepresented class of tetraaryltetrabenzoporphyrins (TATBPs) is investigated thoroughly by DFT calculations, X‐ray diffraction, optical spectroscopy, electro‐ and photochemical studies. Fundamental and unexpected insights were gained about structural and electronic properties of this compound class, which will advance the research around TATPBs based technologies, such as in materials and life sciences.

Abstract

Tetraaryltetrabenzoporphyrins (TATBPs) show, due to their optoelectronic properties, rising potential as dyes in various fields of physical and biomedical sciences. However, unlike in the case of porphyrins, the potential structural diversity of TATBPs has been explored only to little extent, owed mainly to synthetic hurdles. Herein, we prepared a comprehensive library of 30 TATBPs and investigated their fundamental properties. We elucidated structural properties by X‐ray crystallography and found explanations for physical properties such as solubility. Fundamental electronic aspects were studied by optical spectroscopy as well as by electrochemistry and brought in context to the stability of the molecules. Finally, we were able to develop a universal synthetic protocol, utilizing a readily established isoindole synthon, which gives TATBPs in high yields, regardless of the nature of the used arylaldehyde and without meticulous chromatographic purifications steps. This work serves as point of orientation for scientists, that aim to utilize these molecules in materials, nanotechnological, and biomedical applications.

Criss-cross: Incorporation of a phenanthrene moiety into a hexaphyrin(1.1.1.1.1.0) core resulted in an intramolecular ring fusion to give two chiral helicenophyrins. These molecules comprise helicene and porphyrin units.

[Communication]
Bartosz Szyszko, Monika Przewoźnik, Michał J. Białek, Agata Białońska, Piotr J. Chmielewski, Jakub Cichos, Lechosław Latos-Grażyński
Angew. Chem. Int. Ed., March 12, 2018, https://doi.org/10.1002/anie.201800879 Read article

The effect of benzo-fusion on the antiaromaticity of a 16π porphyrin, Ni^II norcorrole, was investigated. The introduction of the benzo groups resulted in significant decrease of the HOMO–LUMO gaps and enhancement of the paratropic ring current effect. Furthermore, Ni^II tetrabenzonorcorrole exhibited singlet diradical character.

[Communication]
Takuya Yoshida, Kohtaro Takahashi, Yuki Ide, Ryohei Kishi, Jun-ya Fujiyoshi, Sangsu Lee, Yuya Hiraoka, Dongho Kim, Masayoshi Nakano, Takahisa Ikeue, Hiroko Yamada, Hiroshi Shinokubo
Angew. Chem. Int. Ed., January 24, 2018, https://doi.org/10.1002/anie.201712961 Read article