PorphyStruct, a new digital tool for the analysis of non‐planar distortion modes of different porphyrinoids, and its application to corrole structures is reported. The program makes use of the normal‐coordinate structure decomposition technique (NSD) and employs sets of normal modes equivalent to those established for porphyrins in order to describe the out‐of‐plane dislocation pattern of perimeter atoms from corroles, norcorroles, porphycenes and other porphyrinoids quantitatively and in analogy to the established terminology. A comparative study of 17 porphyrin structures shows very similar results to the original NSD analysis and no systematic error. Application to corroles is successful and reveals the necessity to implement an extended basis of normal modes for a large share of experimental structures. The results frequently show the concomitant occurence of several modes but remain interpretable. For group XI metal corroles the phenomenon of supersaddling was unravelled, allowing for more in‐depths discussions of structure‐function correlations.

Zinc and cadmium complexes of meso-arylisoporphyrins carrying a pyrrolyl or dipyrrinyl substituent at the sp(3) carbon atom were obtained through a simple one-pot variation of the Alder-Longo porphyrin synthesis. Key to the formation and stabilization of isoporphyrins is the presence of metal acetates during the oxidative macrocyclization step. The characteristic Q-bands of isoporphyrins are found in the NIR region between 750 nm and 880 nm. All of the isolated pyrrolyl- and dipyrrinyl-appended isoporphyrins are stable under typical laboratory conditions and allow chemical transformations like BF2 coordination, transmetalation, and ligand exchange.

A series of pyrrolyl and dipyrrinyl isoporphyrins carrying different phenyl and thienyl groups is reported. The compounds are obtained by a one-pot approach in the presence of a template reagent. Thienyl derivatives gave better yields, and were the only subclass to form with steric hindrance. The structural analyses carried out on compounds 1 and 14 revealed distinct conformational differences which are likely to result from an intramolecular NH … Cl hydrogen bridge of the pyrrolyl subclass. In addition, this hydrogen bridge strongly favors one of the two possible atropisomers. Hindered rotation of the meso-aryl groups is observed only in the cases of methylbenzothienyl derivatives 10 and 15 and leads to the observation of several diastereomers. NIR absorptions up to 923 nm are found throughout. Electrochemical investigations into the 1e À and 2e À reduced species unravel axial ligand exchange dynamics for the zinc isoporphyrin radical, and the probable formation of a zinc phlorinate.

PorphyStruct is a new digital tool that allows quick and easy analyses of hidden conformational features of porphyrinoids from structural data. The software introduces the well‐established technique of normal‐mode structural decomposition (NSD) to porphyrinoids like the corroles, and while retaining the terminology of the NSD method, it is flexible with respect to the size and shape of the macrocycle perimeter. The cover image shows the utopia of a futuristic analysis laboratory where life‐size molecules are analysed for such hidden structural characteristics. More information can be found in the Full Paper by J. Krumsieck and M. Bröring. (DOI: 10.1002/chem.202101243).

Es wurden meso-Arylisoporphyrine mit exocycli-schemP yrrolyl-oder Dipyrrinylsubstituenten am sp 3 -Kohlenstoffatom als Zink-und Cadmiumkomplexeb ei einer Variation der Alder-Longo-Porphyrinsynthese isoliert. Entscheidend bei der Bildung und Stabilisierung dieser Isoporphyrine im Eintopf-Verfahren ist die Gegenwart von Metallacetaten während des Ringschlusses zum Makrocyclus.D ie charakteristi-schenQ -Banden der neuen Isoporphyrine werden erwartungsgemäß im Nah-Infrarot-Bereichz wischen l = 750 und 880 nm gefunden. Alle isolierten Derivate sind stabil an Luft und unter gängigen Laborbedingungen, und erste chemische Transformationen wie BF 2 -Koordination, Transmetallierung oder Ligandenaustauschkonnten durchgeführt werden.