Reaction of [enM(H2O)2](NO3)2 (en = ethylenediamine, M = PdII, PtII) with 2-hydroxypyrimidine (Hpymo) in water results in self-assembly to cyclic complexes of type [enM(pymo-N1,N3)]4(NO3)4 (1, M = PdII; 2, M = PtII) which are structurally analogous to calix[4]arenes. The tetranuclear cations in compounds 1 and 2 adopt, in the solid state, a 1,3-alternate orientation of the pymo residues. Attemp...

We present a straightforward and generally applicable synthesis route for cofacially linked homo- heterobimetallic porphyrin complexes. The protocol allows the of unsymmetrical aryl-based meso-meso as well β-meso-linked porphyrins. Our method significantly increases overall yield published compound known o-phenylene-bisporphyrin (OBBP) by factor 6.8. Besides 16 novel homobimetallic complexes co...

Binuclear diaminocarbene complexes, which form as a regioisomer mixture in the reaction between isocyanide–palladium(II) complex cis-[PdCl2(CNXyl)2] and 1,3-thiazol-2-amine, are able to exchange an anionic chloride ligand with other halides, such Br or I. This process also affords binuclear complexes mixtures of kinetically thermodynamically controlled regioisomers. In CDCl3 solutions, we obser...

Spherical assemblies of the type [PdnL2n]2n+ can be obtained from PdII salts and curved N-donor ligands, L. It is well established that bent angle, α, ligand a decisive factor in self-assembly process, with larger angles leading to complexes higher nuclearity, n. Herein, we report heteroleptic coordination cages [PdnLnL′n]2n+, for which similar correlation between angle nuclearity observed. Tet...

Synthetic self-assembly is a powerful technique for the bottom-up construction of discrete and well-defined polyhedral nanostructures resembling the spherical shape of large biological systems. In recent years, numerous Archimedean-shaped coordination cages have been reported based on the assembly of bent monodentate organic ligands containing two or more distal pyridyl rings and square-planar ...

The geometric structures of Pd-complexes {Pd([9]aneB2A)L2 and Pd([9]aneBAB)L2 where A = P, S; B = N; L = PH3, P(CH3)3, Cl-}, their selective orbital interaction towards equatorial or axial (soft A…Pd) coordination of macrocyclic [9]aneB2A tridentate to PdL2, and electron density transfer from the electron-rich trans L-ligand to the low-lying unfilled a1g(5s)-orbital of PdL2 were investigated us...