RESUMEN
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.
RESUMEN
Stable, long-lived organic cations are directly transferred by electrospray ionization (ESI) from solution into the gas phase where their collision-induced dissociations (CID) are studied by tandem mass spectrometry. Three related types of triphenyl carbenium ions are investigated, in which the meta positions are either substituted by methoxy groups or tertiary nitrogen bridges, including tetramethoxyphenylacridinium (TMPA+ ), dimethoxyquinacridinium (DMQA+ ), and triazatriangulenium (TATA+ ) cations. These ions are triangular in shape with increasing degrees of planarity. Fragmentation occurs at the periphery of the triangular molecule, involving the methoxy groups and the substituent of the nitrogen bridge. Each initial precursor cation is an even electron (EE) system and shows competing dissociations into both even (EE) and odd electron (OE) fragment ions. The latter reaction is a breach of the classic 'even-electron rule' in mass spectrometry. While the EE fragment dissociates similar to the precursor, the OE fragment ion shows a rich radical-induced fragmentation pattern. Two driving forces direct the fragmentation of the EE precursor ion toward OE fragment ions, including the release of stabilized radicals and the extension of the π-system by increasing planarization of the triangulene core. Copyright © 2017 John Wiley & Sons, Ltd.
RESUMEN
A protocol is developed for the coordination of the formate anion (HCOO(-)) to neutral metalloporphyrins (Pors) and -phthalocyanines (Pcs) containing divalent metals as a means to improve their ion formation in electrospray ionization (ESI). This method is particularly useful when the oxidation of the neutral metallomacrocycle fails. While focusing on Zn(II)Pors and Zn(II)Pcs, we show that formate is also readily attached to Mn(II), Mg(II) and Co(II)Pcs. However, for the Co(II)Pc secondary reactions can be observed. Upon collision-induced dissociation (CID), Zn(II)Por/Pc·formate supramolecular complexes can undergo the loss of CO2 in combination with transfer of a hydride anion (H(-)) to the zinc metal center. Further dissociation leads to electron transfer and hydrogen atom loss, generating a route to the radical anion of the Zn(II)Por/Pc without the need for electrochemical reduction, although the Zn(II)Por/Pc may have a too low electron affinity to allow electron transfer directly from the formate anion. In addition to single Por molecules, multi Por arrays were successfully analyzed by this method. In this case, multiple addition of formate occurs, giving rise to multiply charged species. In these multi Por arrays, complexation of the formate anion occurs by two surrounding Por units (sandwich). Therefore, the maximum attainment of formate anions in these arrays corresponds to the number of such sandwich complexes rather than the number of porphyrin moieties. The same bonding motif leads to dimers of the composition [(Zn(II)Por/Pc)2·HCOO](-). In these, the formate anion can act as a structural probe, allowing the distinction of isomeric ions with the formate bridging two macrocycles or being attached to a dimer of directly connected macrocycles.