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A Synthetic Strategy for Cofacial Porphyrin‐Based Homo‐ and Heterobimetallic Complexes
Author(s) -
Schissler Christoph,
Schneider Erik K.,
Felker Benjamin,
Weis Patrick,
Nieger Martin,
Kappes Manfred M.,
Bräse Stefan
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002394
Subject(s) - porphyrin , chemistry , aryl , dimer , crystallography , carbon monoxide , photochemistry , catalysis , alkyl , organic chemistry
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 II 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.