Mn(II) azamacrocyclic bromide complexes with different nuclearities

The coordination behaviour of a series of pyridyl azamacrocyclic ligands, some of them containing cyanomethyl and cyanoethyl pendant-arms, towards Mn(II) ion was studied. All the complexes were characterized by microanalysis, LSI mass spectrometry, IR, UV-Vis spectroscopy and magnetic measurements. Crystal structures of [MnL¹][MnBr₄] (1), [MnL³][MnBr₄] · 2CH₃CN (3), [Mn₂L⁵Br₄] · 2CH₃CN (5) and [Mn₂L⁶Br₄] (6) complexes have been determined. The X-ray studies show the presence of an ionic mixed octahedral-tetrahedral complex for 1 and 2, with the manganese ion of the cation complex, endomacrocyclicly coordinated by the six nitrogen donor atoms from the macrocyclic backbone in a distorted octahedral geometry. Instead, the complexes 5 and 6 are dinuclear, and both manganese ions are coordinated by one pyridinic and two amine nitrogen atoms from the macrocyclic backbone and two bromide ions, being the geometry around the metal better described as distorted square pyramidal. In all cases, the nitrile pendant-arms do not show coordination to the metal ion.     

Synthesis and crystal structures of Cd(II) complexes with di-pyridyl hexa-azamacrocyclic ligands having cyano pendant-arms

The coordination capability of two pendant-armed azamacrocyclic ligands with cyanoethyl L¹and cyanomethyl L² pendant groups towards cadmium nitrate and perchlorate salts was achieved. All metal complexes were characterized by elemental analysis, LSI-MS, IR, conductivity measurements and ¹H NMR spectroscopy. The X-ray crystal structure of the complexes [CdL¹](NO₃)₂, [CdL¹](ClO₄)₂ · CH₃CN, and [CdL²](ClO₄)₂ · H₂O were also determined. All the complexes are mononuclear with the metal ion in a distorted octahedral environment. The pendant groups are not coordinated to the metal due the linear nature of the cyano groups; however, different interactions between nitrate ions, nitrile groups and pyridine rings from the macrocycle have been observed in the Cd(II) complexes with L¹.     

Synthesis of metal complexes with a novel ethyldioxolane pendant-arm hexaazamacrocyclic ligand

The coordination capability of a pendant-arm azamacrocyclic ligand L with four ethyldioxolane pendant groups towards transition, post-transition and lanthanide metal ions was achieved. In all cases, complexes with a 2:1 metal:ligand molar ratio were obtained. The complexes were characterized by elemental analysis, MS-FAB, IR, conductivity measurements, ¹H and ¹³C NMR spectroscopy. Crystal structures of [CoL][CoBr_0.5(NO₃)_3.5] and [(H₂O)H₂L][Nd(NO₃)₄(H₂O)₃]NO₃·3.5H₂O have been determined. The [CoL]²⁺ cation contains the Co(II) ion endomacrocyclicly coordinated in a distorted octahedral geometry with a N₆ core. The Nd(III) complex presents a mononuclear exomacrocyclic structure with an 11 coordination environment. π,π-Stacking interactions have been observed between the pyridine rings of the protonated ligand [(H₂O)H₂L]²⁺, and the [Nd(NO₃)₄(H₂O)₃]²⁻ anion.