A series of mononuclear non-oxido vanadium(IV) [V(IV)(L(1-4))2] (1-4), oxidoethoxido vanadium(V) [V(V)O(L(1-4))(OEt)] (5-8), and dinuclear μ-oxidodioxidodivanadium(V) [V(V)2O3(L(1))2] (9) complexes with tridentate aroylazine ligands are reported [H2L(1) = 2-furoylazine of 2-hydroxy-1-acetonaphthone, H2L(2) = 2-thiophenoylazine of 2-hydroxy-1-acetonaphthone, H2L(3) = 1-naphthoylazine of 2-hydroxy-1-acetonaphthone, H2L(4) = 3-hydroxy-2-naphthoylazine of 2-hydroxy-1-acetonaphthone]. The complexes are characterized by elemental analysis, by various spectroscopic techniques, and by single-crystal X-ray diffraction (for 2, 3, 5, 6, 8, and 9). The non-oxido V(IV) complexes (1-4) are quite stable in open air as well as in solution, and DFT calculations allow predicting EPR and UV-vis spectra and the electronic structure. The solution behavior of the [V(V)O(L(1-4))(OEt)] compounds (5-8) is studied confirming the formation of at least two different types of V(V) species in solution, monomeric corresponding to 5-8, and μ-oxidodioxidodivanadium [V(V)2O3(L(1-4))2] compounds. The μ-oxidodioxidodivanadium compound [V(V)2O3(L(1))2] (9), generated from the corresponding mononuclear complex [V(V)O(L(1))(OEt)] (5), is characterized in solution and in the solid state. The single-crystal X-ray diffraction analyses of the non-oxido vanadium(IV) compounds (2 and 3) show a N2O4 binding set and a trigonal prismatic geometry, and those of the V(V)O complexes 5, 6, and 8 and the μ-oxidodioxidodivanadium(V) (9) reveal that the metal center is in a distorted square pyramidal geometry with O4N binding sets. For the μ-oxidodioxidodivanadium species in equilibrium with 5-8 in CH2Cl2, no mixed-valence complexes are detected by chronocoulometric and EPR studies. However, upon progressive transfer of two electrons, two distinct monomeric V(IV)O species are detected and characterized by EPR spectroscopy and DFT calculations.

The synthesis of ethoxido-bridged dinuclear oxidovanadium(IV) complexes of the general formula (HNEt)[(VOL)(μ-OEt)] (1-3) with the azo dyes 2-(2'-carboxy-5'-X-phenylazo)-4-methylphenol (HL, X = H; HL, X = NO) and 2-(2'-carboxy-5'-Br-phenylazo)-2-naphthol (HL) as ligands is reported. The ligands differ in the substituents at the phenyl ring to probe their influence on the redox behavior, biological activity, and magnetochemistry of the complexes, for which the results are presented and discussed. All synthesized ligands and vanadium(IV) complexes have been characterized by various physicochemical techniques, namely, elemental analysis, electrospray ionization mass spectrometry, spectroscopic methods (UV/vis and IR), and cyclic voltammetry. X-ray crystallography of 1 and 3 revealed the presence of a twisted arrangement of the edged-shared bridging core unit. In agreement with the distorted nature of the twisted core, antiferromagnetic exchange interactions were observed between the vanadium(IV) centers of the dinuclear complexes with a superexchange mechanism operative. These results have been verified by DFT calculations. The complexes were also screened for their in vitro cytotoxicity against HeLa and HT-29 cancer cell lines. The results indicated that all the synthesized vanadium(IV) complexes (1-3) were cytotoxic in nature and were specific to a particular cell type. Complex 1 was found to be the most potent against HeLa cells (IC value 1.92 μM).

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Four novel dimeric bis-μ-imido bridged metal-metal bonded oxidomolybdenum(V) complexes [MoOL'] (1-4) (where L' are rearranged ligands formed in situ from HL) and a new mononuclear dioxidomolybdenum(VI) complex [MoOL] (5) synthesized from salen type NO ligands are reported. This rare series of imido-bridged complexes (1-4) have been furnished from rearranged HL' ligands, containing an aromatic diimine (o-phenylenediamine) "linker", where Mo assisted hydrolysis followed by -C═N bond cleavage of one of the arms of the ligand HL took place. A monomeric molybdenum(V) intermediate species [MoO(HL')(OEt)] (I) was generated in situ. The concomitant deprotonation and dimerization of two molybdenum(V) intermediate species (I) ultimately resulted in the formation of a bis-μ-imido bridge between the two molybdenum centers of [MoOL'] (1-4). The mechanism of formation of 1-4 has been discussed, and one of the rare intermediate monomeric molybdenum(V) species I has been isolated in the solid state and characterized. The monomeric dioxidomolybdenum(VI) complex [MoOL] (5) was prepared from the ligand HL where the aromatic "linker" was replaced by an aliphatic diimine (1,2-diaminopropane). All the ligands and complexes have been characterized by elemental analysis, IR, UV-vis spectroscopy, NMR, ESI-MS, and cyclic voltammetry, and the structural features of 1, 2, 4, and 5 have been solved by X-ray crystallography. The DNA binding and cleavage activity of 1-5 have been explored. The complexes interact with CT-DNA by the groove binding mode, and the binding constants range between 10 and 10 M. Fairly good photoinduced cleavage of pUC19 supercoiled plasmid DNA was exhibited by all the complexes, with 4 showing the most promising photoinduced DNA cleavage activity of ∼93%. Moreover, in vitro cytotoxic activity of all the complexes was evaluated by MTT assay, which reveals that the complexes induce cell death in MCF-7 (human breast adenocarcinoma) and HCT-15 (colon cancer) cell lines.

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