Five octahedral ruthenium(II) complexes with azoimine–quinoline (Azo) and α-diimine (L) ligands having the general formula [Ru
II(L)(Azo)Cl](PF
6) (
1–
5) {Azo: PhN=NC(COMe)=NC
9H
6N, L = 4,4′-dimethoxy-2,2′-bipyridine (dmeb) (
1), 4,4′-di-tertbutyl-2,2′-bipyridine (dtb) (
2), 1,10-phenanthroline (phen) (
3), 5-chlorophenanthroline (Clphen) (
4), or 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen)
(5)} were prepared by stepwise addition of the tridentate azoimine (H
2Azo) and α-diimine (L) pro-ligands to RuCl
3 in refluxing EtOH. The tridentate azoimine–quinoline ligands coordinate to ruthenium via the Azo-
N′,
N′-imine and
N″-quinolone nitrogen atoms. The spectroscopic properties (IR, UV/Vis,
1H,
13C and
19F NMR) and electrochemical behavior of complexes
1–
5 and the X-ray crystal structures of complexes
2 and
3 are presented. The coordination of Ru(II) to these strong π-acceptor ligands (Azo and L) results in a large anodic shift for the Ru(III/II) couples of 1.63–1.72 V versus NHE. The electronic spectra in MeCN and IR spectra in CH
2Cl
2 for complex
3 in its oxidized
3 + and reduced
3 ? forms were investigated. The calculated absorption spectrum of
3 in MeCN was used to assign the UV–Vis absorption bands.
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