The newly prepared homo-bimetallic complexes [M2(imda)2(H2O)4], [M2(imda)2(Bipy)2] (M = Co, Ni or Cu) and [Fe2(imda)2(H2O)3Cl] (H2imda = iminodiacetic acid and Bipy = 2,2′-bipyridine) have been studied employing IR, FAB-mass, 1H and 13C NMR, EPR and ligand field spectra, which indicated a high-spin state of metal ion with hexa-coordinate environment. 57Fe Mössbauer data of the homo-bimetallic complex [Fe2(imda)2(H2O)3Cl] confirm a high-spin configuration with Fe (±3/2 → 1/2) nuclear transitions and the presence of Kramer's double degeneracy. At RT, the spin–spin interactions of the neighbouring nuclei (Fe3+–Fe3+ = S5/2–S5/2) are anti-ferromagnetically coupled. However, at LNT, the complex acquires a mixed-valent [FeIII–FeII] composition corroborated from the X-band EPR data. CV studies indicated the presence of quasi-reversible redox CuII/I, CuII/III, FeIII/II, FeIII/I and FeII/I couples. 相似文献
Spectral and molecular model computations on homo-dinuclear complexes [M2L2(H2O)2Cl2] [L = 1-(salicylaldeneamino)-3-hydroxypropane, M = Cr3+, Mn3+, Fe3+, Co3+, Ni3+ or Cu3+] are consistent with a distorted hexa-coordinate geometry. X-band EPR spectral data indicated a rhombic distortion around Cu(II) ion. Magnetic moment and 57Fe Mössbauer data confirmed a high-spin state electronic configuration (t2g3eg2, S = 5/2) and asymmetric ligand environment around Fe(III) with nuclear transitions Fe(±3/2 → 1/2) exhibiting Kramer's double degeneracy. The neighboring Fe(III) nuclei in the homo-dinuclear species are antiferromagnetically coupled. 相似文献
We report the synthesis and crystallographic studies of paddlewheel-based methyl cobaloxime assembly formed from methyl cobaloxime, isonicotinic acid, and Zn(NO(3))(2). The cobaloxime units are assembled over two-dimensional metal-organic polyhedra constructed from isonicotinate and Zn metal ions. 相似文献
Two novel dinuclear organotin(IV) complexes [n-Bu2Sn(imda)(H2O)]2·Bipy (1) and [n-Bu2Sn(imda)(H2O)]2·Phen (2) [H2imda = iminodiacetic acid, Bipy = 2,2′-bipyridine and Phen = 1,10-phenanthroline] were synthesised and characterized employing IR, 1H, 13C, 119Sn NMR, and 119Sn Mössbauer spectroscopic and elemental analyses. Single crystal X-ray crystallography of 1 has confirmed that it is a binuclear Sn(IV) species formed via carboxylate bridges where each metal adopted a seven coordinate distorted pentagonal bipyramidal geometry. The iminodiacetate dianion (imda2−) acts as a potential tridentate [N,O,O] carboxylate bridging ligand. The packing revealed that the additional α-diimine (Bipy or Phen) does not coordinate to metal ion. However, its presence in the crystal lattice as spacer helps for the formation of a supramolecular framework by bringing the two binuclear species close enough through extensive H-bonding. The in vitro cytotoxicity of compounds 1 and 2 indicate better results than cisplatin against three tumor cell lines investigated. 相似文献
The FTIR and FT-Raman spectra of tetrahydroxy-1,4quinone hydrate have been recorded in the regions 4000–400 and 3500–50 cm–1 respectively. Using the observed Fourier-transform infrared spectroscopy (FTIR) and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound has been carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by the density functional theory (DFT/B3LYP) and Hartree–Fock (HF) method with 6-311+G(d,p) basis set. The difference between the observed and scaled wavenumber values of most of the fundamental vibrations is very small. A detailed interpretation of the infrared and Raman spectra of tetrahydroxy-1,4quinone hydrate is also reported. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. 相似文献
The bimetallic complexes [M2LCl4] (M = Cr, Co, Ni, Cu) prepared via metal template cyclization reactions were characterized by physico-chemical and spectroscopic methods. L is a 30-membered [N10] macrocycle with tetraamide functions bind metal ions through aza donors forming hexa-coordinate geometry. The perspective view and important structural parameters have been computed from the molecular model (MOPAC) method. The electrochemical studies indicate existence of quasi-reversible redox couples in solution. The metal complexes were screened (in vitro) against a few pathogenic fungi and bacteria to assess their growth inhibiting potential. 相似文献
Reactions of a 32-membered [N12] macrocyclic ligand, L.2HClO4 with metal salts MCl3 (M=Cr or Fe) and MCl2 (M=Co, Ni or Cu) have produced complexes of stoichiometries M2LCl4(ClO4)2 and M2LCl2(ClO4)2, respectively. However, reactions with [M(Ph3P)2Cl2] (M=Co or Ni) and [(η5-C5H5)Ni(Ph3P)I] follow a ligand substitution path resulting in products with stoichiometries M2LCl2(ClO4)2 and [(η5-C5H5)2Ni2L(ClO4)2], respectively. The mode of bonding and geometry of the complexes have been derived on the basis of i.r., ligand field spectral
and magnetic susceptibility measurements. EPR of CuII complex shows anisotropy with
, G < 4.0 and orbital reduction factor
. Thermodynamic first ionic association constants (K1) and the corresponding free energy change (ΔG) of complexes in DMSO have been determined and discussed. Cyclic voltammetric studies indicate the presence of a quasi-reversible
redox couples CrIII/II, CoII/I, NiII/I, NiII/III and CuII/I in solutions suggesting flexible nature of the macrocyclic cavity. 相似文献
Synthesis and structural characterization of two heterodinuclear ZnII-LnIII complexes with the formula [ZnLn(HL)(µ-OAc)(NO3)2(H2O)x(MeOH)1-x]NO3 · n H2O · n MeOH [Ln?=?Pr (1), Nd (2)] and the crystal and molecular structure of [ZnNd(HL)(µ-OAc)(NO3)2(H2O)] [ZnNd(HL)(OAc)(NO3)2(H2O)](NO3)2 · n H2O · n MeOH (3) are reported. The asymmetrical compartmental ligand (E)-2-(1-(2-((2-hydroxy-3-methoxybenzylidene)amino)-ethyl)imidazolidin-2-yl)-6-methoxyphenol (H2L) is formed from N1,N3-bis(3-methoxysalicylidene)diethylenetriamine (H2valdien) through intramolecular aminal formation, resulting in a peripheral imidazoline ring. The structures of 1–3 were revealed by X-ray crystallography. The smaller ZnII ion occupies the inner N2O2 compartment of the ligand, whereas the larger and more oxophilic LnIII ions are found in the outer O2O2’ site.
Graphic Abstract
Synthesis and structural characterization of two heterodinuclear ZnII-LnIII complexes (Ln?=?Pr, Nd) bearing an asymmetrical compartmental ligand formed in situ from N1,N3-bis(3-methoxysalicylidene)diethylenetriamine (H2valdien) through intramolecular aminal formation are reported.
The homo-bimetallic complexes of stoichiometry Fe2(L)ClO4(ClO4)2 where L are novel unsymmetrical [N10] (L1.2HClO4) and [N12] (L2.2HClO4) macrocyclic ligands, have been prepared. The ligands were obtained from an in situ capping reaction of the reactive substrate, N,N'-bis(N-ethylaniline)hydrazine-1,2-diimine with a mixture of aniline or 1,3-diaminopropane and HCHO in presence of HClO4. The compounds have been characterized by elemental analyses, conductometric, IR, FAB-mass and electronic spectral studies. IR data of complexes suggest coordination from unsymmetrical aza sites as a tridentate (N,N,N) or tetradentate (N,N,N,N) ligand. mu(eff) values of the complexes suggest presence of antiferromagnetically coupled (Fe3+-Fe3+=S5/2-S5/2) spin exchange. M?ssbauer parameters of the complexes support (+/-3/2)-->(+/-1/2) nuclear transition in high-spin configurations of Fe(III) nuclei of the homo-bimetallic complexes with the presence of Kramer's double degeneracy. 相似文献