title: Self-assembly of ligands designed for the building of a new type of [2 x 2] metallic grid. anion encapsulation and diffusion NMR spectroscopy.
abstract: The ligands 4,6-bis(pyrazol-1-yl)pyrimidine (bpzpm), 4,6-bis(3,5-dimethylpyrazol-1-yl)pyrimidine (bpz(*)pm), 4,6-bis(4-methylpyrazol-1-yl)pyrimidine (Mebpzpm), and 3,6-bis(3,5-dimethylpyrazol-1-yl)pyridazine (ppdMe) were synthesized and were made to react with Cu(I) centers in the presence of different counteranions. Different [2 x 2] metallic grids were obtained. With ligands bpzpm, bpz*pm, and Mebpzpm, a new type of grid was obtained where the facing ligands were divergent and two counteranions (BF(4-) or PF(6-)) were hosted in the resulting cavities and exhibit C-H...F and anion...pi interactions in the solid state. The presence of methyl groups on the pyrazolyl rings induced several distortions in the structure. In complexes with the ligand ppdMe, there were found two groups of parallel ligands in the grid, and the cavities generated were smaller. The counteranions were situated outside the grid, and the facing ligands exhibited aromatic pi-pi stacking interactions. Anion-pi interactions involving the pyridazine ring were found. The behavior in solution of the new derivatives with a special emphasis on the cation-anion interactions was studied by UV-vis and NMR spectroscopy. Diffusion NMR experiments performed for some complexes allowed us to conclude that weak cation-anion interactions exist in solution, with the counteranions undergoing fast exchange on the diffusion time scale between the free and ion-paired states.
authors.affiliation: Departamento de Química InorgAnica, OrgAnica y Bioquímica, Facultad de Químicas, IRICA, Universidad de Castilla-La Mancha, Avda Camilo José Cela, 10, E-13071 Ciudad Real, Spain. Blanca.Manzano@uclm.es
authors.forename: Blanca R
authors.initials: BR
authors.lastname: Manzano
authors.forename: Félix A
authors.initials: FA
authors.lastname: Jalón
authors.forename: Isabel M
authors.initials: IM
authors.lastname: Ortiz
authors.forename: M Laura
authors.initials: ML
authors.lastname: Soriano
authors.forename: Felipe Gómez de la
authors.initials: FG
authors.lastname: Torre
authors.forename: José
authors.initials: J
authors.lastname: Elguero
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Maestro
authors.forename: Kurt
authors.initials: K
authors.lastname: Mereiter
authors.forename: Tim D W
authors.initials: TD
authors.lastname: Claridge
mesh_terms: D000838:Anions; D018360:Crystallography, X-Ray; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000838:Anions; D008024:Ligands; D008670:Metals