Structure and Properties of a Five-Coordinate Nickel(II) Porphyrin.

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ID: 43380
2019
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Abstract
Axial coordination in nickel(II) porphyrins has been thoroughly investigated and is well understood. However, isolated five-coordinate nickel(II) porphyrins are still elusive after 50 years of intense research, even though they play a crucial role as intermediates in enzymes and catalysts. Herein we present the first fully stable, thoroughly characterized five-coordinate nickel(II) porphyrin in solution and in the solid state (crystal structure). The spectroscopic properties indicate pure high-spin behavior ( S = 1). There are distinct differences in the NMR, UV-vis, and redox behavior compared to those of high-spin six-coordinate [with two axial ligands, such as NiTPPF·(py)] and low-spin four-coordinate (NiTPPF) nickel(II) porphyrins. The title compound, a strapped nickel(II) porphyrin, allows a direct comparison of four-, five-, and six-coordinate nickel(II) porphyrins, depending on the environment. With this reference in hand, previous results were reevaluated, for example, the switching efficiencies and thermodynamic data of nickel(II) porphyrin-based spin switches in solution.
Reference Key
gutzeit2019structureinorganic Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors Gutzeit, Florian;Dommaschk, Marcel;Levin, Natalia;Buchholz, Axel;Schaub, Eike;Plass, Winfried;Näther, Christian;Herges, Rainer;
Journal Inorganic chemistry
Year 2019
DOI
10.1021/acs.inorgchem.9b00348
URL
Keywords
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