Solid State and Solution Study on the Formation of Inorganic Anion Complexes with a Series of Tetrazine-Based Ligands
Matteo Savastano,
Celeste García-Gallarín,
Claudia Giorgi,
Paola Gratteri,
Maria Dolores López de la Torre,
Carla Bazzicalupi,
Antonio Bianchi,
Manuel Melguizo
Affiliations
Matteo Savastano
Department of Chemistry “Ugo Schiff”, University of Florence, Via della Lastruccia, 3-13, 50019 Sesto Fiorentino, Italy
Celeste García-Gallarín
Department of Inorganic and Organic Chemistry, University of Jaén, 23071 Jaén, Spain
Claudia Giorgi
Department of Chemistry “Ugo Schiff”, University of Florence, Via della Lastruccia, 3-13, 50019 Sesto Fiorentino, Italy
Paola Gratteri
Department of NEUROFARBA-Pharmaceutical and Nutraceutical Section, and Laboratory of Molecular Modeling Cheminformatics & QSAR, University of Florence, Via Ugo Schiff 6, 50019 Sesto Fiorentino, Italy
Maria Dolores López de la Torre
Department of Inorganic and Organic Chemistry, University of Jaén, 23071 Jaén, Spain
Carla Bazzicalupi
Department of Chemistry “Ugo Schiff”, University of Florence, Via della Lastruccia, 3-13, 50019 Sesto Fiorentino, Italy
Antonio Bianchi
Department of Chemistry “Ugo Schiff”, University of Florence, Via della Lastruccia, 3-13, 50019 Sesto Fiorentino, Italy
Manuel Melguizo
Department of Inorganic and Organic Chemistry, University of Jaén, 23071 Jaén, Spain
Four molecules (L1−L4) constituted by an s-tetrazine ring appended with two identical aliphatic chains of increasing length bearing terminal morpholine groups were studied as anion receptors in water. The basicity properties of these molecules were also investigated. Speciation of the anion complexes formed in solution and determination of their stability constants were performed by means of potentiometric (pH-metric) titrations, while further information was obtained by NMR and isothermal titration calorimetry (ITC) measurements. The crystal structures of two neutral ligands (L3, L4) and of their H2L3(ClO4)2∙2H2O, H2L4(ClO4)2∙2H2O, H2L3(PF6)2, and H2L3(PF6)2∙2H2O anion complexes were determined by single crystal X-ray diffraction. The formation of anion−π interactions is the leitmotiv of these complexes, both in solution and in the solid state, although hydrogen bonding and/or formation of salt-bridges can contribute to their stability. Evidence of the ability of these ligands to form anion−π interactions is given by the observation that even the neutral (not-protonated) molecules bind anions in water to form complexes of significant stability, including elusive OH− anions.
