Testing the limits of halogen bonding in coordination chemistry (CROSBI ID 245284)
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Podaci o odgovornosti
Borovina, Mladen ; Kodrin, Ivan ; Đaković, Marijana
engleski
Testing the limits of halogen bonding in coordination chemistry
In order to link coordination complexes via halogen bonds, and to test the limit of halogen-bond interaction in metal-containing crystalline solids, a series of thirteen new acac complexes of CoII and NiII with small halogen-bearing aromatic ligands, namely 3-halopyridines, 2-halopirazines and 5-halopyrimidine was prepared. Ligands having a single aromatic ring were used to limit the influence of pi-stacking on the resulting crystal structure, while the fine-tuning of electron density at the halogen atom sigma-hole was achieved via two routes: (i) by changing the position of additional nitrogen heteroatom on the aromatic ring, and (ii) by utilizing different transition metal ions. The moderate ‘activation’ of the halogen atom produced the desired halogen interaction in a limited number of supramolecular events. Two supramolecular links, C-X...O and C-H...O, were shown to have a larger influence on the overall supramolecular assembly, and their role could be explained on the basis of calculated molecular electrostatic potential values. Slight electronic changes introduced by the metal-cation exchange revealed an additional handle for achieving a switch between different supramolecular interactions and architectures.
halogen bond ; hydrogen bond ; coordination compounds, nickel(II), cobalt(II)
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