Halide and hydroxide anion binding in water

The formation of halide and hydroxide anion complexes with two ligands L1 (3,6 bis(morpholin-4-ylmethyl)-1,2,4,5-tetrazine) and L2 (3,6-bis(morpholin-4-ylethyl)-1,2,4,5-tetrazine) was studied in aqueous solution, by means of potentiometric and ITC procedures. In the solid state, HF2−, Cl− and Br− co...

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Autores: Savastano, Matteo, Bazzicalupi, Carla, García-Gallarín, Celeste, Giorgi, Claudia, López-de-la-Torre, María Dolores, Pichierri, Fabio, Bianchi, Antonio, Melguizo, Manuel
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Institución:Universidad de Jaén
Repositorio:RUJA. Repositorio Institucional de la Producción Científica de la Universidad de Jaén
OAI Identifier:oai:ruja.ujaen.es:10953/2059
Acceso en línea:https://hdl.handle.net/10953/2059
Access Level:acceso abierto
Palabra clave:Tetrazines
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spelling Halide and hydroxide anion binding in waterSavastano, MatteoBazzicalupi, CarlaGarcía-Gallarín, CelesteGiorgi, ClaudiaLópez-de-la-Torre, María DoloresPichierri, FabioBianchi, AntonioMelguizo, ManuelTetrazinesThe formation of halide and hydroxide anion complexes with two ligands L1 (3,6 bis(morpholin-4-ylmethyl)-1,2,4,5-tetrazine) and L2 (3,6-bis(morpholin-4-ylethyl)-1,2,4,5-tetrazine) was studied in aqueous solution, by means of potentiometric and ITC procedures. In the solid state, HF2−, Cl− and Br− complexes of H2L22+ were analysed by single crystal XRD measurements. Further information on the latter was obtained with the use of density functional theory (DFT) calculations in combination with the polarizable continuum model (PCM). The presence of two halide or bifluoride HF2− (F–H–F−) anions forming anion–π interactions, respectively above and below the ligand tetrazine ring, is the leitmotiv of the [(H2L2)X2] (X = HF2, Cl, Br, I) complexes in the solid state, while hydrogen bonding between the anions and protonated morpholine ligand groups contributes to strengthen the anion–ligand interaction, in particular in the case of Cl− and Br−. In contrast to the solid state, only the anion : ligand complexes of 1 : 1 stoichiometry were found in solution. The stability of these complexes displays the peculiar trend I− > F− > Br− > Cl− which was rationalized in terms of electrostatic, hydrogen bond, anion–π interactions and solvent effects. DFT calculations performed on [(H2L2)X]+ (X = F, Cl, Br, I) in PCM water suggested that the ligand assumes a U-shaped conformation to form one anion–π and two salt bridge interactions with the included anions and furnished structural information to interpret the solvation effects affecting complex formation. The formation of hydroxide anion complexes with neutral (not protonated) L1 and L2 molecules represents an unprecedented case in water. The stability of the [L(OH)]− (L = L1, L2) complexes is comparable to or higher than the stability of halide complexes with protonated ligand molecules, their formation being promoted by largely favourable enthalpic contributions that prevail over unfavourable entropic changes.Financial support from the Italian MIUR (project 2015MP34H3) and from the Spanish MINECO (project MAT2014-60104-C2-2-R) is gratefully acknowledged. The centre of instrumental facilities, STI, of the University of Jaén is acknowledged for technical assistance. FP acknowledges the Department of Applied Chemistry of the Graduate School of Engineering of Tohoku University for financial support.Royal Society of Chemistry202420242018info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/10953/2059reponame:RUJA. Repositorio Institucional de la Producción Científica de la Universidad de Jaéninstname:Universidad de JaénInglésDalton TransactionsCC0 1.0 Universalhttp://creativecommons.org/publicdomain/zero/1.0/info:eu-repo/semantics/openAccessoai:ruja.ujaen.es:10953/20592026-06-24T12:41:07Z
dc.title.none.fl_str_mv Halide and hydroxide anion binding in water
title Halide and hydroxide anion binding in water
spellingShingle Halide and hydroxide anion binding in water
Savastano, Matteo
Tetrazines
title_short Halide and hydroxide anion binding in water
title_full Halide and hydroxide anion binding in water
title_fullStr Halide and hydroxide anion binding in water
title_full_unstemmed Halide and hydroxide anion binding in water
title_sort Halide and hydroxide anion binding in water
dc.creator.none.fl_str_mv Savastano, Matteo
Bazzicalupi, Carla
García-Gallarín, Celeste
Giorgi, Claudia
López-de-la-Torre, María Dolores
Pichierri, Fabio
Bianchi, Antonio
Melguizo, Manuel
author Savastano, Matteo
author_facet Savastano, Matteo
Bazzicalupi, Carla
García-Gallarín, Celeste
Giorgi, Claudia
López-de-la-Torre, María Dolores
Pichierri, Fabio
Bianchi, Antonio
Melguizo, Manuel
author_role author
author2 Bazzicalupi, Carla
García-Gallarín, Celeste
Giorgi, Claudia
López-de-la-Torre, María Dolores
Pichierri, Fabio
Bianchi, Antonio
Melguizo, Manuel
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Tetrazines
topic Tetrazines
description The formation of halide and hydroxide anion complexes with two ligands L1 (3,6 bis(morpholin-4-ylmethyl)-1,2,4,5-tetrazine) and L2 (3,6-bis(morpholin-4-ylethyl)-1,2,4,5-tetrazine) was studied in aqueous solution, by means of potentiometric and ITC procedures. In the solid state, HF2−, Cl− and Br− complexes of H2L22+ were analysed by single crystal XRD measurements. Further information on the latter was obtained with the use of density functional theory (DFT) calculations in combination with the polarizable continuum model (PCM). The presence of two halide or bifluoride HF2− (F–H–F−) anions forming anion–π interactions, respectively above and below the ligand tetrazine ring, is the leitmotiv of the [(H2L2)X2] (X = HF2, Cl, Br, I) complexes in the solid state, while hydrogen bonding between the anions and protonated morpholine ligand groups contributes to strengthen the anion–ligand interaction, in particular in the case of Cl− and Br−. In contrast to the solid state, only the anion : ligand complexes of 1 : 1 stoichiometry were found in solution. The stability of these complexes displays the peculiar trend I− > F− > Br− > Cl− which was rationalized in terms of electrostatic, hydrogen bond, anion–π interactions and solvent effects. DFT calculations performed on [(H2L2)X]+ (X = F, Cl, Br, I) in PCM water suggested that the ligand assumes a U-shaped conformation to form one anion–π and two salt bridge interactions with the included anions and furnished structural information to interpret the solvation effects affecting complex formation. The formation of hydroxide anion complexes with neutral (not protonated) L1 and L2 molecules represents an unprecedented case in water. The stability of the [L(OH)]− (L = L1, L2) complexes is comparable to or higher than the stability of halide complexes with protonated ligand molecules, their formation being promoted by largely favourable enthalpic contributions that prevail over unfavourable entropic changes.
publishDate 2018
dc.date.none.fl_str_mv 2018
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/10953/2059
url https://hdl.handle.net/10953/2059
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Dalton Transactions
dc.rights.none.fl_str_mv CC0 1.0 Universal
http://creativecommons.org/publicdomain/zero/1.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv CC0 1.0 Universal
http://creativecommons.org/publicdomain/zero/1.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:RUJA. Repositorio Institucional de la Producción Científica de la Universidad de Jaén
instname:Universidad de Jaén
instname_str Universidad de Jaén
reponame_str RUJA. Repositorio Institucional de la Producción Científica de la Universidad de Jaén
collection RUJA. Repositorio Institucional de la Producción Científica de la Universidad de Jaén
repository.name.fl_str_mv
repository.mail.fl_str_mv
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