No abstract

Es wird über Darstellung einer Anzahl Additions‐ und Substitutionsverbindungen des Vanadintetrachlorids, Vanadintrichlorids und Vanadindichlorids mit sauerstoff‐ und stickstoffhaltigen organischen Verbindungen berichtet.

Umsetzungen des Galliumtrichlorids mit sauerstoffhaltigen organischen Verbindungen werden untersucht und Darstellungsvorschriften für die dabei entstehenden Additions‐ und Substitutionsverbindungen gegeben.

One dinuclear and one 1D polymeric nickel(II) complex, namely {[Ni2(HL)2(pa)2(H2O)2]•DMF} (1) and {[Ni2(HL)2(ppda)(H2O)2]•DMF•H2O}n (2) (H2L = (E)-2-((1-hydroxybutan-2ylimino)methyl)phenol, pa = 3-phenylacrylate, ppda = p-phenylenediacrylate) have been synthesized and characterized by X-ray single crystal structure determination. Complex 1 is double phenoxo-bridged dinuclear Ni(II) complex, whereas complex 2 is a 1D polynuclear chain where double phenoxo-bridged dinuclear units are connected through bridging ppda ligands. The variable temperature magnetic behavior of the complexes was studied using the Hamiltonian H = −JS1S2, S1 = S2 = SNi and confirms the presence of an overall antiferromagnetic interaction in both complexes. Good agreement between the experimental and simulated curves were found using the parameters: gNi = 2.15, DNi = 4.0 cm−1 and JNi-Ni = −0.60 cm−1 for 1, and gNi = 2.15, DNi = 4.8 cm−1 and JNi-Ni = −3 cm−1 for 2. The interactions of the complexes with CT-DNA were investigated using UV-Vis absorption and fluorescence spectroscopic methods and they show that both the complexes interact with CT-DNA. The intrinsic binding constants values for interaction with CT-DNA are 3.9(±0.10) × 105 and 3.43(±0.09) × 105 M−1 for 1 and 2, respectively. The interactions of the complexes with bovine serum albumins (BSA) and human serum albumins (HSA) were also studied using electronic absorption and fluorescence spectroscopic techniques and the results show that both complexes interact with the serum albumins via a ground state association process.

Distorted square pyramidal complexes [Cu(L1)(H2O)]·ClO4 (1), [Cu(L2)(H2O)]·ClO4 (2) and [Cu(L3)(H2O)]·ClO4 (3) (HL1 = o-{[2-(2-aminoethylamino)ethylimino]methyl}phenol; HL2 = 2-{[2-(2-aminoethylamino)ethylimino]methyl}-6-methoxyphenol; HL3 = o-{1-[2-(2-aminoethylamino)ethylimino]ethyl}phenol) have been synthesized, and characterized by X-ray crystallography and spectroscopic analysis. All the complexes exhibit fluorescence at room temperature [λex = 267 nm, λem = 312, 329 and 357 nm, φ = 0.52 for 1; λex = 272 nm, λem = 312, 329 and 355 nm, φ = 0.46 for 2; λex = 265 nm, λem = 312, 356 and 377 nm, φ = 0.33 for 3]. The electronic structure and photophysical properties of the ligands and complexes were calculated by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods using the B3LYP, B3PW91 and MPW1PW91 functionals, with 6-31G (d-p) and LanL2DZ basis sets. The results of TD-DFT calculations are functional-dependent and among the functionals, B3LYP was able to best reproduce the experimental results. Catecholase activity of 1-3 has been investigated using 3,5-di-tert butyl catechol (3,5-DTBC) as the model substrate and found that complexes are active for catalyzing the aerobic oxidation of 3,5-DTBC to 3,5-di-tert butyl benzoquinone (3,5-DTBQ). The compound with more distorted square pyramidal geometry shows a higher rate of catalytic activity. All the complexes have been tested for their anticancer activities in human breast (MCF7) cancer cell lines. Complexes show dose dependent suppression of cell viability with IC50 values 30, 68 and >100 μM for 1, 2 and 3, respectively. Anticancer activities of 1-3 and cisplatin were compared, and found that 1-3 were relatively less active than cisplatin