PorphyStruct: A Digital Tool for the Quantitative Assignment of Non‐Planar Distortion Modes in Four‐Membered Porphyrinoids

Abstract

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.

Nonplanar porphyrins: synthesis, properties, and unique functionalities

“…3) and is available online for numeric interrogations of novel structures or databases. 20,21 NSD is discussed further in the structural section.…”

Helicity Modulation in NIR‐Absorbing Porphyrin‐Ryleneimides

“…The curvature is induced by the mismatch between the ionic radius and the diameter of the macrocyclic core, which can occasionally result in dramatic deformations in oligopyrrolic macrocycles [62] . A very significant doming distortion component of 0.822 Å was determined for D 4 ‐ 2 ‐Cd(H 2 O) (Table S1) [55] . The latter value is much larger than typically observed in pentacoordinate Cd II porphyrins, in which it rarely exceeds 0.5 Å.…”

“…The vertical extent of the π system is particularly small in D 4 ‐ 3 ‐Zn (0.46 Å), possibly reflecting the rigidifying effect of metal coordination. The porphyrin substructures in D 4 ‐ 3 ‐H 2 and D 4 ‐ 3 ‐Zn show a combination of “propellering” (0.48 Å) and saddling distortion (0.48–0.51 Å, Table S1) [55] . The cadmium analogue was isolated in the solid state in the form of D 4 ‐ 3 ‐Cd(py), with a pyridine ligand bound apically to the metal center.…”

“…3-H 2 pyridine-d 5 S1). [55] The cadmium analogue was isolated in the solid state in the form of D 4 -3-Cd(py), with a pyridine ligand bound apically to the metal center. The doming distortion in this species is much smaller than in D 4 -2-Cd(H 2 O).…”

1,3-Dipolar cycloaddition of polycyclic azomethine ylide to norcorroles: towards dibenzoullazine-fused derivatives

“…1). We analyzed the out-of-plane norcorrole ring distortions by means of PorphStruct tool 44 which is based on the normal-coordinate structure decomposition (NSD) 45,46 (Table S18 and Fig. S136-S143 in ESI †).…”