RESUMO
The self-assembly of [Co(MeTPyA)(CH3COO)]PF6 (1) and [Fe(bbp)(CN)3]2- affords a cyanido-bridged square-shaped {Fe2Co2} tetranuclear complex, [{Co(MeTPyA)(µ2-NC)2Fe(bbp)(CN)}2]·3H2O (2; MeTPyA = tris((3,5-dimethylpyrazol-1-yl)methyl)amine and H2bbp = bis(2-benzimidazolyl)pyridine). The possibility of inducing an intramolecular electron transfer coupled spin transition in 2 by employing protonation as an external stimulant is explored. UV-visible spectrophotometric measurements, electrochemical and 1H NMR studies establish that a reversible intramolecular electron transfer coupled spin transition can be triggered in 2 upon addition of either acid or base.
RESUMO
Flexible hexatopic ligands, 1,2,3,4,5,6-hexakis(1H-naphtho[2,3-d]imidazol-1-ylmethyl)benzene (L(2)) and 1,2,3,4,5,6-hexakis(4,5-diphenylimidazol-1-ylmethyl)benzene (L(3)), containing six neutral naphthanoimidazolyl and 4,5-diphenylimidazolyl N donors were synthesized and used to assemble M6L6L'-type [M = Re(CO)3, L = anionic angular rigid NN donors, and L' = flexible hexatopic N donors] spheroid metallacycles. These molecules with a diameter of â¼17 Å were obtained from Re2(CO)10, H-L (imidazole, benzimidazole, and naphthanoimidazole), and L' [1,2,3,4,5,6-hexakis(benzimidazol-1-ylmethyl)benzene (L(1)), L(2), and L(3)] in a one-step process. Ligands L(2) and L(3) were characterized by elemental analysis, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and (1)H NMR spectroscopy. Metallacycles 1-5 were characterized by elemental analysis, ESI-TOF-MS, Fourier transform infrared spectroscopy, and single-crystal X-ray diffraction analysis. Molecules 1, 2, and 4 can be considered as metallocavitands and contain multiple solvent-accessible receptors, i.e., two metallocalix[3]arene units and six/four calix[4]arene-/cleft-shaped receptors, on the surface. Guests such as acetone molecules could be accommodated in the calix[4]arene/cleft-shaped receptor of the metallocavitands.
RESUMO
We report an easily recoverable and reusable versatile magnetic catalyst (Fe3O4@CS_AgNi, where CS = chitosan) for organic reduction reactions. The catalytic system is prepared by dispersing AgNi bimetallic nanoparticles on the magnetite core-shell (Fe3O4@CS). The as-synthesized catalyst has been characterized by spectroscopic techniques, such as IR, UV-vis, and X-ray photoelectron spectroscopy (XPS), and analytical tools, such as thermogravimetric analysis, powder X-ray diffraction, Brunauer-Emmett-Teller adsorption, FEG-scanning electron microscopy, high-resolution transmission electron microscopy (HR-TEM), inductively coupled plasma-atomic emission spectroscopy, and magnetic measurements. HR-TEM studies indicate the core-shell structure of Fe3O4@CS and confirm the presence of AgNi nanoparticles on the surface of Fe3O4@CS spheres. IR spectral and XPS studies lend evidence for the occurrence of a strong chemical interaction between the amino groups of CS and AgNi nanoparticles. The nano-catalyst Fe3O4@CS_AgNi rapidly reduces p-nitrophenol to p-aminophenol using NaBH4 as the reductant within a few minutes under ambient conditions (as monitored by UV-visible spectroscopy). The utility of this catalytic system has also been extended to the reduction of other nitroarenes. A strong interaction between Fe3O4@CS and AgNi nanoparticles impedes the leaching of AgNi nanoparticles from the core-shell support, leading to excellent reusability of the catalyst.
RESUMO
Bridgeless double metallocalix[4]arenes possessing two orthogonally arranged dinuclear cavitands were obtained from a Re2(CO)10, rigid bis-chelating OO donor (H2-L), and a flexible bis-ditopic NN donor (L') by a one-pot approach.