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Synthesis, Characterization, and Electrochemistry of the Manganese(I) Complexes of meso ‐Substituted [14]Tribenzotriphyrins(2.1.1)
Author(s) -
Xue Zhaoli,
Wang Yemei,
Mack John,
Zhu Weihua,
Ou Zhongping
Publication year - 2015
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.201405135
Subject(s) - chemistry , cyclic voltammetry , redox , crystallography , manganese , porphyrin , single crystal , metal , electron transfer , electrochemistry , absorption spectroscopy , yield (engineering) , ligand (biochemistry) , homo/lumo , photochemistry , spectroscopy , metalation , inorganic chemistry , stereochemistry , molecule , materials science , electrode , organic chemistry , biochemistry , physics , receptor , quantum mechanics , metallurgy
Metalation of 6,13,20,21‐tetraaryl‐22 H ‐[14]tribenzotriphyrins(2.1.1) (TriP, 1 a – d ) with [Mn(CO) 5 Br] provided Mn I tricarbonyl complexes of [14]tribenzotriphyrins(2.1.1) 2 a – d in 85–93 % yield. The complexes were characterized by mass spectrometry and UV/Vis absorption, IR, and NMR spectroscopy. Single‐crystal X‐ray analyses revealed that 2 b and 2 c adopt bowl‐shaped conformations. The redox properties of [(TriP)Mn I (CO) 3 ] ( 2 a – d ) were studied by cyclic voltammetry. Each compound undergoes two reversible one‐electron reductions to form a porphyrin π anion radical and a dianion in CH 2 Cl 2 . Two oxidation waves were observed, the first of which corresponds to a metal‐centered electron‐transfer process. The redox potentials of 2 a – d are consistent with the optical spectroscopic data and the relatively narrow HOMO–LUMO gaps that were predicted in DFT calculations. The optical spectra can be assigned by using Michl’s perimeter model. TDDFT calculations predict the presence of several metal‐to‐ligand charge‐transfer bands in the L‐band region between 500 and 700 nm.