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Increasing the π–π Interactions in Trinuclear Ni II 3 Triplesalophen Complexes
Author(s) -
Oldengott Jan,
Röhs Fridolin L. B.,
Stammler Anja,
Bögge Hartmut,
Glaser Thorsten
Publication year - 2017
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201700118
Subject(s) - pyridine , steric effects , chemistry , ligand (biochemistry) , crystallography , crystal structure , molecule , stereochemistry , solvent , medicinal chemistry , organic chemistry , receptor , biochemistry
The new triplesalophen ligand H 6 kruse Br was synthesized as a variation of the triplesalophen ligands H 6 baron R by replacing a phenyl by a methyl group at the terminal ketimine in order to allow closer contacts of trinuclear complexes due to less steric hindrance by the smaller methyl group. The ligand H 6 kruse Br was used to synthesize the trinuclear complex [(kruse Br )Ni II 3 ], which is insoluble in organic solvents despite the coordinating solvent pyridine. Recrystallization from pyridine results in the complex [(kruse Br ){Ni 2 (Ni(py) 2 )}], which was characterized by single‐crystal X‐ray diffraction. Two Ni II ions are four‐coordinate by the salophen‐like subunits while the third Ni II ion is six‐coordinate by two additional pyridine donors. The analysis of the molecular and crystal structure in comparison to that of Ni II 3 complexes of (baron R ) 6– reveals that the methyl group in [(kruse Br ){Ni 2 (Ni(py) 2 )}] results in less ligand folding and in closer contact distance of two Ni II 3 complexes by π – π interactions of 3.2 Å. This indicates that trinuclear complexes of H 6 kruse Br are more suitable than complexes of H 6 baron R as molecular building blocks for the anticipated synthesis of nonanuclear single‐molecule magnets.