[Ag 4 (bpzqnx) 5 ] n (BF 4 ) 4n (5)

1. FORMATION OF MACROSTRUCTURES WITH THE LIGANDS 3,6-BIS(3,5-DIMETHYLPYRAZOL-1-YL)PYRIDAZINE AND 4,6-BIS(PYRAZOL-1-YL)PYRIMIDINE M. Laura Soriano1, Félix A. Jalón1, Blanca R. Manzano1, Isabel M. Ortiz1, Kurt Mereiter2, Tim D. W. Claridge3 1Departamento de Química Inorgánica, Orgánica y Bioquímica, UCLM, Facultad de Químicas, Avda. Camilo J. Cela, 10, 13071 Ciudad Real. 2Faculty of Technical Chemistry, Vienna University of Technology, Getreidemarkt 9/164-SC, A-1060 Vienna, Austria. 3 Chemistry Research Laboratory, 12 Mansfield Road, Oxford OX1 3TA, England Introduction NMR solution study A recent feature in the development and progress of chemical research has been the concern with molecular assemblies, ensembles, and all manner of structured aggregates. In our researcher group we have designed some [2x2] grids by the mixture of polyazine ligands and metal salts of Cu(I), Cu(II) and Co(II) at room temperature. In order to promote the formation of hosts with different size and shape in their cavities we used two types of bitopic bispyrazolylazines that contain two pyrazolyl rings in different sites of the main heterocycle, in particular the 3,6-(3,5-dimethylpyrazol-1-yl)pyridazine and 4,6-(3,5-dimethylpyrazol-1-yl)pyrimidine. For complex 1, 2 and 3. Although the counteranion is not allowed to keep inside the cationic moieties it remains around them with close distances (2,25 Å) indicating that there is a weak intermolecular interaction in solution. By 19F, 1H-HOESY we have determined that PF6 is close to the the H4,5 of the pyridazine ring and less closed to the Me5 of the pyrazole ring in accordance with the X-ray studies. [Cu(bpz*pdz)]4(PF6)4 (1) SYNTHESIS OF LIGANDS SHAPE OF THE GRIDS H4,5 (pyridazine) FORMATION OF THE [2 x 2] GRIDS For complexes 4-6 the size and shape of the cavity allow the wrapping of two of the counteranions. It has not been possible to study the intermolecular interactions in solution for those complexes because of their lower solubility. • X-Ray Structures of Complexes 4-6: • The organic components are divergent and form [2x2] non conventional grids. • The inner cavity is bigger than in 1-3. • Finally, it is worth noting that two of the counteranions for the grids of 4-6 were located within the cavity in the solid state with hydrogen bonding interactions. • The cobalt complex, 4, has 3 OH and 1 H2O bridging two Co atoms. • X-Ray Structures of Complexes 1 and 3: • The organic components have a parallel orientation leading to the formation of [2x2] conventional grids. • The organic components are mutually shifted in order to reduce the steric hindrance between the Me groups of the pyrazole rings. • The inner cavity is too small to guest molecules. [Ag4(bpzqnx)5]n(BF4)4n (5) [Cu(bpz*pdz)(PF6)]41 [Cu(bpz*pdz)(CH3-C6H4-SO3)]43 [Co4(bpz*pdz)4(H2O)(OH)3(ClO4)5] 4 [Cu(bpzpm)(PF6)]45