ABSTRACT
The hitherto unavailable free-base tripyrrins HTrpy have been prepared by cyanide promoted demetallation of a nickel(ii) tripyrrin and by acid-induced condensation of a diformylpyrrole and an alkylpyrrole with a sterically shielded alpha-position.
ABSTRACT
Etheral solutions of free base tripyrrins (HTrpy) were prepared by treatment of nickel isocyanate complexes (TrpyNiNCO) with excess cyanide. From these solutions sensitive metallotripyrrins with cobalt(II), iron(II), and manganese(II) ions (TrpyMX) and with a choice of external ligands X could be obtained in pure, crystalline form. Four cobalt and one iron chelate were characterized by X-ray crystallography. Tetracoordinate cobalt(II) species with X = I, NCO, and NCS displayed unstrained tetrahedral coordination geometries, whereas the pentacoordinate TrpyCoNO3 with the O,O-nitrato ligand narrows a trigonal bipyramidal coordination. TrpyFeNCO undergoes a redox-transformation to (TrpyFeNCO)2O upon crystallization and was structurally characterized as this with an almost linear Fe-O-Fe subunit. Donor association was studied by UV-vis spectroscopy employing different solvents and showed that TrpyMnX and TrpyFeX species are very prone to the formation of pentacoordinate species, whereas TrpyCoX compounds have an intermediate tendency to do so. Nevertheless, complex fragments of all three metal ions form 1D coordination polymers with dicyanamido ligands, which were investigated by means of IR and SQUID measurements.
ABSTRACT
Neutral transition metal complexes of different alpha,omega-dimethyltripyrrins TrpyMX with M = Cu(II) and Zn(II) have been prepared with a variety of anionic halogeno and pseudohalogeno ligands X, and have been studied with respect to coordination modes and structural distortion. Only four- and five-coordinate species have been observed throughout the series. All four-coordinate species display unstrained, but distorted tetrahedral or strained and distorted square-planar coordination environments for zinc(II) and copper(II) species, respectively, thus following the expectations from simple ligand field arguments. Five-coordinate species do not form easily and were observed either in donor solvents or in the solid as 1D coordination polymers with distorted trigonal-bipyramidal coordination and different topologies.
ABSTRACT
Sterically hindered nickel- tripyrrins [Ni(trpy)X] with different di-, tri- and tetradentate anions X have been prepared with the aim of finding coordination polymers formed by self-association. The syntheses were performed by simple ligand-exchange reactions and proceeded successfully with the pseudohalides CN(-), OCN(-), SCN(-), SeCN(-), N(CN)(2) (-) (dicyanoamido, dca) and C(CN)(3) (-) (tricyanomethanido, tcm), the cyanidometallates [Ag(CN)(2)](-) and [Ni(CN)(4)](2-) and the salicylate anion (sal(-)). X-ray crystallographic analyses revealed that the complexes with cyanido and isocyanato ligands, as well as the compound with a salicylato ligand, are prototypes for structurally distinct monomeric species in the solid state, whereas one-dimensional coordination polymers or supramolecular three-dimensional networks are formed from all other combinations. The polymeric compounds display a variety of individual pillar and network architectures with functionalised pores and clefts and with the Ni(trpy) fragments in different relative orientations. Hydrogen bonding and pi stacking were found to be additional structure-directing effects, which increased the structural complexity of the system. The Ni(trpy) subunit has thus been proven to be a versatile building block for the construction of supramolecular assemblies and metal organic frameworks (MOFs) from pentacoordinate Ni(II) ions.
