Gas‐Phase Transformation of Fluorinated Benzoporphyrins to Porphyrin‐Embedded Conical Nanocarbons. Issue 53 (2nd September 2020)

• Record Type: Journal Article
• Authors: Lungerich, Dominik; Hitzenberger, Jakob Felix; Ruppel, Michael; Döpper, Tibor; Witt, Matthias; Ivanović‐Burmazović, Ivana; Görling, Andreas; Jux, Norbert; Drewello, Thomas
• Is Part Of: Chemistry. Volume 26:Issue 53(2020)
• Page Start: 12180
• Page End: 12187
• Publication Date: 2020-09-02
• Subjects: annulenes -- C−F activation -- collision-induced dissociation -- mass spectrometry -- polycyclic aromatic hydrocarbons -- porphyrinoids; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202002638
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Geodesic nitrogen‐containing graphene fragments are interesting candidates for various material applications, but the available synthetic protocols, which need to overcome intrinsic strain energy during the formation of the bowl‐shaped skeletons, are often incompatible with heteroatom‐embedded structures. Through this mass spectrometry‐based gas‐phase study, we show by means of collision‐induced dissociation experiments and supported by density functional theory calculations, the first evidence for the formation of a porphyrin‐embedded conical nanocarbon. The influences of metalation and functionalization of the used tetrabenzoporphyrins have been investigated, which revealed different cyclization efficiencies, different ionization possibilities, and a variation of the dissociation pathway. Our results suggest a stepwise process for HF elimination from the fjord region, which supports a selective pathway towards bent nitrogen‐containing graphene fragments. Abstract : Porphyrin in a cone ! The preparation of a porphin at the tip of a carbon nanocone has been achieved by the transformation of fluorinated tetraaryltetrabenzoporphyrins in the gas phase through collision‐induced dissociation. In this process, a remarkable selectivity of fjord ‐region C−F activation was found. These findings allow considering novel strategies to access this type of nitrogen‐containing carbon allotrope and to apply them in novel hybrid materials.