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Spin Transition and Charge Transfer in Co2+/Co3+ Complexes of Meridional Ligands Holding Nearby Redox‐active Triarylamine

Title data

Schnaubelt, Linda ; Petzold, Holm ; Speck, J. Matthäus ; Rüffer, Tobias ; Hörner, Gerald ; Lang, Heinrich:
Spin Transition and Charge Transfer in Co2+/Co3+ Complexes of Meridional Ligands Holding Nearby Redox‐active Triarylamine.
In: Zeitschrift für anorganische und allgemeine Chemie. Vol. 644 (15 November 2018) Issue 21 . - pp. 1257-1267.
ISSN 0044-2313
DOI: https://doi.org/10.1002/zaac.201800274

Project information

Project financing: Deutsche Forschungsgemeinschaft

Abstract in another language

Phenanthroline‐pyridyl bases containing a triarylamine (Tara) 1 –4 and their respective Co2+ ([Co(L )2](ClO4)2, L = 1 –4 ) and Co3+ complexes ([Co(L )2](ClO4)3–n (BF4)n , L = 2 , 3 ) were prepared. The structure of [Co(3 )2](ClO4)2 in the solid state was determined by single‐crystal X‐ray diffractometry. The oxidation processes of [Co(L )2](ClO4)2 (L = 1 –4 ) were investigated by cyclic voltammetry. The first oxidation step in [Co(L )2](ClO4)2 (L = 1 –3 ) is chemically reversible and cobalt‐centered. This process is followed by the irreversible oxidation of the Tara units at higher potentials. In case of [Co(4 )2](ClO4)2 the first oxidation is Tara‐centered and electrochemically reversible. The electronic coupling between the Co3+ ion and Tara in in‐situ prepared [Co(L )2]3+ (L = 2 , 3 ) was investigated by UV/Vis/NIR spectroelectrochemistry. In spectra of in situ prepared [Co(L )2]3+ (L = 2 , 3 ) ligand‐to‐metal charge transfer (LMCT) bands were found between 600–1250 nm, which were assigned to a charge transfer from the Tara to the Co3+ ion. Physical parameters (wavenumber ν̃max, extinction ε max, and full‐width at half‐maximum Δν1/2) of the charge transfer (CT) bands were obtained by deconvolution of the UV/Vis/NIR spectra. In addition analogous Co3+ complexes [Co(L )2]3+ (L = 2 , 3 ) were isolated as the mixed BF4–/ClO4– salts. These compounds exhibit the same CT bands as observed in the in situ oxidation experiments.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV > Chair Inorganic Chemistry IV - Univ.-Prof. Dr. Birgit Weber
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Result of work at the UBT: No
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 06 Jul 2020 07:28
Last Modified: 06 Jul 2020 07:28
URI: https://eref.uni-bayreuth.de/id/eprint/55690