Add time:08/21/2019 Source:sciencedirect.com
Treatment of two equivalents of N,N′-bis(X-phenyl)oxamides (1) with one equivalent of [Zn(OAc)2(H2O)2] (2) in the presence of four equivalents of [nBu4N]OH produce the corresponding bis(N,N′-substituted oxamate) zincate(II) complexes with the general formula (nBu4N)2[Zn(X-phenyloxamide)2] (3) (a, X = 3-NO2; b, X = 4-NO2; c, X = 2,6 CH3; d, X = 3,4-CH3; e, X = 2-Br; f, X = 4-Br; g, X = 2-F; h, X = 4-F; i, X = 2-Cl; j, X = H). Complexes 3a–j have been characterized by elemental analysis, NMR (1H, 13C{1H}) and IR spectroscopy. In addition, 3a and 3f have been characterized by single crystal X-ray crystallography. The zinc (II) ion in the later complexes is four-coordinate with two ethanediamide-nitrogen atoms from two bidentate N,N′-disubstituted oxamate ligands at each metal center. In addition, the calculated electrostatic potentials of 3f rationalize the formation of chain structures via the Br…Br interaction. Complexes 3a–j showed a characteristic LLCT (π → π*) band in the UV-Vis spectra, which was confirmed by TD-DFT calculations. DFT calculations show that the Zn(II) orbitals are neither contributing to the HOMO nor to the LUMO, i.e. the HOMO and LUMO are mainly located on the ligands. The emission spectra analyses for Zn(II) complexes 3a–j show enhanced intensity and blue shifted emission compared to ligands 1a−j. The cyclic voltammetry measurements of complexes 3a–j showed reversible electrochemical processes for the (N,N′-substituted oxamate−2/−3) between −1.52 and −1.77 V using [NnBu4][B(C6F5)4] as the supporting electrolyte. It was found that the 3-nitro- (3a) and 4-nitro-functionalized (3b) derivatives resulted in a significantly higher Fc/Fc+ redox potential (E0′) compared to the more electron-rich 3, 4-dimethyl (3c) and 2,6-dimethyl (3d) derivatives.
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