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Coordination‐Induced Spin‐State Switching of an Aminyl‐Radical‐Bridged Nickel(II) Porphyrin Dimer between Doublet and Sextet States
- Source :
- Angewandte Chemie. 131:5077-5081
- Publication Year :
- 2019
- Publisher :
- Wiley, 2019.
-
Abstract
- A bis(NiII -porphyrinyl)aminyl radical with meso-C6 F5 groups was prepared as a spin-delocalized stable aminyl radical with a doublet spin state. Upon addition of pyridine, both NiII centers became hexacoordinated by accepting two axial pyridines, which triggered a spin-state change of the NiII centers from diamagnetic (S=0) to paramagnetic (S=1). The resulting high-spin NiII centers interact with the aminyl radical ferromagnetically to give rise to an overall sextet state (S=5/2). Importantly, this coordination-induced spin-state switching can be conducted in a reversible manner, in that washing of the high-spin radical with aqueous hydrochloric acid regenerates the original doublet radical in good yield.
- Subjects :
- Aqueous solution
Spin states
010405 organic chemistry
Dimer
Radical
chemistry.chemical_element
General Chemistry
General Medicine
010402 general chemistry
01 natural sciences
Porphyrin
Catalysis
0104 chemical sciences
chemistry.chemical_compound
Nickel
Paramagnetism
Crystallography
chemistry
Pyridine
Subjects
Details
- ISSN :
- 15213757 and 00448249
- Volume :
- 131
- Database :
- OpenAIRE
- Journal :
- Angewandte Chemie
- Accession number :
- edsair.doi.dedup.....dd839e3942b3bb9d2ba7f6755c6bdb6a