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A Synthetic Strategy for Cofacial Porphyrin-Based Homo- and Heterobimetallic Complexes

Schissler, Christoph; Schneider, Erik K.; Felker, Benjamin; Weis, Patrick; Nieger, Martin; Kappes, Manfred M.; Bräse, Stefan

Abstract:
We present a straightforward and generally applicable synthesis route for cofacially linked homo‐ and heterobimetallic porphyrin complexes. The protocol allows the synthesis of unsymmetrical aryl‐based meso‐meso as well as β‐meso‐linked porphyrins. Our method significantly increases the overall yield for the published compound known as o‐phenylene‐bisporphyrin (OBBP) by a factor of 6.8. Besides the synthesis of 16 novel homobimetallic complexes containing Mn$^{III}$, Fe$^{III}$, Ni$^{II}$, Cu$^{II}$, Zn$^{II}$, and Pd$^{II}$, we achieved the first single‐crystal X‐ray structure of an unsymmetrical cofacial benzene‐linked porphyrin dimer containing both planar‐chiral enantiomers of a Ni$^{III}$$_{2}$ complex. Additionally, this new methodology allows access to heterobimetallic complexes such as the Fe$^{III}$‐Ni$^{II}$ containing carbon monoxide dehydrogenase active site analogue. The isolated species were investigated by various techniques, including ion mobility spectrometry, DFT calculations, and UV/Vis spectroscopy. This allowed us to probe the influence of interplane distance on Soret band splitting.

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Verlagsausgabe §
DOI: 10.5445/IR/1000129544
Veröffentlicht am 10.02.2021
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Organische Chemie (IOC)
Institut für Physikalische Chemie (IPC)
Institut für Biologische und Chemische Systeme (IBCS)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2021
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000129544
Erschienen in Chemistry - a European journal
Verlag Wiley
Band 27
Heft 9
Seiten 3047-3054
Nachgewiesen in Dimensions
Scopus
Web of Science
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