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Please use this identifier to cite or link to this item: http://hdl.handle.net/10651/7606

Title: Ligand-to-metal charge transfer resulting in metalloaromaticity of [R,R-Cyclohexyl-1,2-bis(2-Oxidonaphthylideneiminato-N,N',O,O')]Cu(II): A scrutinized structural investigation
Author(s): Karabiyik, Hasan
Erdem, Özlem
Aygün, Muhittin
Güzel, Bilgehan
García-Granda, Santiago
Keywords: Metalloaromaticity. Valence Tautomerism. Bis(Tetradentate) Schiff Base Ligand. Ligand-To-Metal Charge Transfer (Lmct) Complex. Homa
Issue date: 2010
Publisher version: http://dx.doi.org/10.1007/s10904-009-9323-3
Citation: Journal of Inorganic and Organometallic Polymers and Materials, 20(1), p. 142-151 (2010); doi:10.1007/s10904-009-9323-3
Format extent: p. 142-151
Abstract: Molecular and crystal structure analysis of a tetradentate ligand-to-metal charge transfer (LMCT) complex, [R,R-cyclohexyl-1,2-bis(2-oxidonaphthylideneiminato- N,N0,O,O0)]Cu(II), are described and characterized by X-ray crystallography and FTIR spectroscopy. The Cu(II) centers are coordinated by four atoms of the donor set [N2O2] in a distorted square-planar fashion, which can be attributed to an active electronic delocalization within metallacycles and polychelating property of the pro-ligand. Bond valences of copper centers in four crystallographically independent monomers are slightly distinguished from each other, which is associated with differences in charge delocalization levels of the pro-ligands. Total valence of the copper center is increased with increasing p-electron donation from naphthalene fragments to metallacycles. This charge transfer leads to p···p interactions between metallacycles including imine bridges. In addition, decreases in the centroid–centroid distances of p···p interactions are associated with increased aromatic character of metallacycles. Molecules of the complex are stacked as dimers in the crystal structure formed by p···p interactions and aggregations of these dimeric formations along a-axis are strengthened by C–H···Otype H-bonds and C–H···p interactions.
URI: http://hdl.handle.net/10651/7606
ISSN: 1574-1443
Local identifier: 20100390
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