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Alejandro Macías

Publications and source records attributed to Alejandro Macías.

4 recordsLinked to original sources

Different nuclearity silver(I) complexes with novel tetracyano pendant-armed hexaazamacrocyclic ligands.

A new series of different nuclearity silver(I) complexes with a variety of tetracyano pendant-armed hexaazamacrocyclic ligands containing pyridine rings (Ln) has been prepared starting from the nitrate and perchlorate Ag(I) salts in acetonitrile solutions. The ligands and complexes were characterized by microanalysis, conductivity measurements, IR, Raman, electronic absorption and emission spectroscopy, and L-SIMS spectrometry. (1)H NMR titrations were employed to investigate silver complexation by ligands L3 and L.(4) The compounds [Ag2L2(NO3)2] (2), ([Ag2L2](ClO4)2.2CH3CN)(infinity) (4), [AgL3](ClO(4)).CH3CN (5), and [Ag4(L4)2(NO3)2](NO3)2.4CH3CN.2H2O (7) were also characterized by single-crystal X-ray diffraction. The complexes have different nuclearities. Complex 2 is dinuclear with an {AgN3O2} core and a significant intermetallic interaction, whereas complex 4 has a polymeric structure formed by dinuclear distorted {AgN4} units joined by nitrile pendant arms. Compound 5 is mononuclear with a distorted {AgN2} linear geometry, and complex 7 consists of discrete units of a tetranuclear array of silver atoms with {AgN3O} and {AgN4} cores in distorted square planar environments. Complexes 2 and 4 were found to be fluorescent in the solid state at room temperature because of the Ag-Ag interactions.

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Pentanuclear Ba(II) complex of a macrocyclic ligand.

We report here the first pentanuclear Ba(II) complex of a new tri-aza, tri-oxa macrocycle with two carboxymethyl "arms" pending from two N atoms, H2L2. The crystal structure corresponds to the formula [Ba5(H0.375L2)4(ClO4)(CH3CH2OH)(H2O)2](ClO4)2.5 x 9.5H2O and reveals the presence of four molecules of the ligand surrounding five Ba(II) ions, giving rise to an unusual structure with the metal ions inside a spherical organic cavity.

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Metal complexes with a new N(4)O(3) amine pendant-armed macrocyclic ligand: synthesis, characterization, crystal structures, and fluorescence studies.

The synthesis of a new oxaaza macrocyclic ligand, L, derived from O(1),O(7)-bis(2-formylphenyl)-1,4,7-trioxaheptane and tren containing an amine terminal pendant arm, and its metal complexation with alkaline earth (M = Ca(2+), Sr(2+), Ba(2+)), transition (M = Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+)), post-transition (M = Pb(2+)), and Y(3+) and lanthanide (M = La(3+), Er(3+)) metal ions are reported. Crystal structures of [H(2)L](ClO(4))(2).3H(2)O, [PbL](ClO(4))(2), and [ZnLCl](ClO(4)).H(2)O are also reported. In the [PbL] complex, the metal ion is located inside the macrocyclic cavity coordinated by all N(4)O(3) donor atoms while, in the [ZnLCl] complex, the metal ion is encapsulated only by the nitrogen atoms present in the ligand. pi-pi interactions in the [H(2)L](ClO(4))(2).3H(2)O and [PbL](ClO(4))(2) structures are observed. Protonation and Zn(2+), Cd(2+), and Cu(2+) complexation were studied by means of potentiometric, UV-vis, and fluorescent emission measurements. The 10-fold fluorescence emission increase observed in the pH range 7-9 in the presence of Zn(2+) leads to L as a good sensor for this biological metal in water solution.

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Barium Templating Schiff-Base Lateral Macrobicycles.

Schiff-base lateral macrobicycles containing two different binding units, a rigid and unsaturated N(2)X set (X: N, O) and a flexible and cyclic N(2)O(n)() set, linked by two aromatic bridges, have been prepared by reaction of the appropriate bibracchial diamines N,N'-bis(aminobenzyl)-diaza-crown and diformyl precursors in the presence of Ba(II) as templating agent. The expected cryptands do not form in the absence of the cation; the presence of this metal ion is necessary to orient the diamine precursor in a syn conformation. Comparison of the X-ray crystal structures of the barium complex of the bibracchial diamine N,N'-bis(2-aminobenzyl)-1,10-diaza-15-crown-5 and the barium complex of the cryptand derived from it incorporating a pyridine unit indicates that the encapsulation of the metal ion is clearly more effective in the case of the cryptand. The coordination of Ba(II) ion to the pyridine nitrogen atom promotes the displacement of the metal into the cavity of the cryptand as well as important changes in the conformation of the crown unit, although the fold of the pendant arms remains practically unchanged. The cryptands reported constitute the first example of a novel family of macrobicycles.

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