Protonated forms of the tetrazine ligand L2 (3,6-bis(morpholin-4-ylethyl)-1,2,4,5-tetrazine) interact with iodide in aqueous solution forming relatively stable complexes (G° = -11.6(4) kJ/mol for HL2+ + I- = (HL2)I and G° = -13.4(2) kJ/mol for H2L22+ + I- = [(H2L2)I]+). When solutions of [(H2L2)I]+ are left in contact with the air, crystals of the oxidation product (H2L2)2(I3)3I.4H2O are formed. Unfortunately, the low solubility of I3- complexes prevents the determination of their stability constants. The crystal structures of H2L2I2.H2O (1), H2L2(I3)2.2H2O (2) and (H2L2)2(I3)3I.4H2O (3) were determined by means of X-ray diffraction analyses. In all crystal structures, it was found that the interaction between I- and I3- with H2L22+ is dominated by anion interactions with the π electron density of the receptor. Only in the case of 1, the iodide anions involved in close anion-π interactions with the ligand tetrazine ring form an additional H-bond with the protonated morpholine nitrogen of an adjacent ligand molecule. Conversely, in crystals of 2 and in 3 there are alternated segregated planes which contain only protonated ligands hydrogen-bonded to cocrystallized water molecules or I3- and I- forming infinite two-dimensional networks established through short interhalogen contacts, making these crystalline products good candidates to behave as solid conductors. In the solid complexes, the triiodide anion displays both end-on and side-on interaction modes with the tetrazine ring, in agreement with density functional theory calculations indicating a preference for the alignment of the I3- molecular axis with the molecular axis of the ligand. Further information about geometries and structures of triiodide anions in 2 and 3 were acquired by the analysis of their Raman spectra.

Iodide and triiodide anion complexes involving anion–π interactions with a tetrazine-based receptor / Savastano, Matteo; Bazzicalupi, Carla; García, Celeste; Gellini, Cristina; López de la Torre, María Dolores; Mariani, Palma; Pichierri, Fabio; Bianchi, Antonio; Melguizo, Manuel. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - STAMPA. - 46:(2017), pp. 4518-4529. [10.1039/C7DT00134G]

Iodide and triiodide anion complexes involving anion–π interactions with a tetrazine-based receptor

SAVASTANO, MATTEO;BAZZICALUPI, CARLA;GELLINI, CRISTINA;MARIANI, PALMA MARIA;BIANCHI, ANTONIO;
2017

Abstract

Protonated forms of the tetrazine ligand L2 (3,6-bis(morpholin-4-ylethyl)-1,2,4,5-tetrazine) interact with iodide in aqueous solution forming relatively stable complexes (G° = -11.6(4) kJ/mol for HL2+ + I- = (HL2)I and G° = -13.4(2) kJ/mol for H2L22+ + I- = [(H2L2)I]+). When solutions of [(H2L2)I]+ are left in contact with the air, crystals of the oxidation product (H2L2)2(I3)3I.4H2O are formed. Unfortunately, the low solubility of I3- complexes prevents the determination of their stability constants. The crystal structures of H2L2I2.H2O (1), H2L2(I3)2.2H2O (2) and (H2L2)2(I3)3I.4H2O (3) were determined by means of X-ray diffraction analyses. In all crystal structures, it was found that the interaction between I- and I3- with H2L22+ is dominated by anion interactions with the π electron density of the receptor. Only in the case of 1, the iodide anions involved in close anion-π interactions with the ligand tetrazine ring form an additional H-bond with the protonated morpholine nitrogen of an adjacent ligand molecule. Conversely, in crystals of 2 and in 3 there are alternated segregated planes which contain only protonated ligands hydrogen-bonded to cocrystallized water molecules or I3- and I- forming infinite two-dimensional networks established through short interhalogen contacts, making these crystalline products good candidates to behave as solid conductors. In the solid complexes, the triiodide anion displays both end-on and side-on interaction modes with the tetrazine ring, in agreement with density functional theory calculations indicating a preference for the alignment of the I3- molecular axis with the molecular axis of the ligand. Further information about geometries and structures of triiodide anions in 2 and 3 were acquired by the analysis of their Raman spectra.
2017
46
4518
4529
Savastano, Matteo; Bazzicalupi, Carla; García, Celeste; Gellini, Cristina; López de la Torre, María Dolores; Mariani, Palma; Pichierri, Fabio; Bianchi, Antonio; Melguizo, Manuel
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Utilizza questo identificatore per citare o creare un link a questa risorsa: https://hdl.handle.net/2158/1079362
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