Issue 48, 2021

Spin-state control of cobalt(ii) and iron(ii) complexes with click-derived tripodal ligands through non-covalent and fluorine-specific interactions

Abstract

The fine-tuning of intermolecular or intramolecular non-covalent interactions (NCIs) and thus the precise synthesis of metal complexes in which the spin states can be controlled by NCIs remains challenging, even though several such complexes have been intensively studied. In this regard, we present mononuclear cobalt(II) and iron(II) complexes with “click”-derived tripodal ligands that contain fluorinated benzyl substituents in the secondary coordination sphere. The complexes were co-crystallized with different solvent molecules to decipher the effect of the crystallized solvents on NCIs, and on the spin state of the metal ion. Additionally, the fluorine-specific interactions in the secondary coordination sphere were examined. We present a first structure-property correlation between the nature of interaction of the (per)fluorinated aromatic substituents on the ligand periphery, and the spin state of the metal complexes. In particular, the TF5TA containing ligand show interesting stacking motifs depending on the used solvent, and these interactions have an influence on the spin state of the cobalt(II) complexes. Furthermore, the iron(II) complex thereof, Fe(TF5TA)2(BF4)2·2EtOH displays spin crossover (SCO).

Graphical abstract: Spin-state control of cobalt(ii) and iron(ii) complexes with click-derived tripodal ligands through non-covalent and fluorine-specific interactions

Supplementary files

Article information

Article type
Paper
Submitted
19 okt 2021
Accepted
19 nov 2021
First published
22 nov 2021

Dalton Trans., 2021,50, 18097-18106

Spin-state control of cobalt(II) and iron(II) complexes with click-derived tripodal ligands through non-covalent and fluorine-specific interactions

M. Nößler, D. Hunger, F. Reichert, M. Winkler, M. Reimann, J. Klein, S. Suhr, L. Suntrup, J. Beerhues, M. Kaupp, J. van Slageren and B. Sarkar, Dalton Trans., 2021, 50, 18097 DOI: 10.1039/D1DT03535E

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