Assembly of Polyiodide Networks with Cu(II) Complexes of Pyridinol-Based Tetraaza Macrocycles
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Assembly of Polyiodide Networks with Cu(II) Complexes of Pyridinol-Based Tetraaza Macrocycles

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Assembly of Polyiodide Networks with Cu(II) Complexes of Pyridinol-Based Tetraaza Macrocycles

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dc.contributor.author Martínez Camarena, Álvaro
dc.contributor.author Savastano, Matteo
dc.contributor.author Blasco Llopis, Salvador
dc.contributor.author Delgado Pinar, Estefanía
dc.contributor.author Giorgi, Claudia
dc.contributor.author Bianchi, Antonio
dc.contributor.author Garcia-España Monsonis, Enrique
dc.contributor.author Bazzicalupi, Carla
dc.date.accessioned 2022-04-29T13:35:47Z
dc.date.available 2022-04-29T13:35:47Z
dc.date.issued 2022
dc.identifier.uri https://hdl.handle.net/10550/82470
dc.description.abstract Polyiodide networks are currently of great practical interest for the preparation of new electronic materials. The participation of metals in the formation of these networks is believed to improve their mechanical performance and thermal stability. Here we report the results on the construction of polyiodide networks obtained using Cu(II) complexes of a series of pyridinol-based tetraazacyclophanes as countercations. The assembly of these crystalline polyiodides takes place from aqueous solutions on the basis of similar structural elements, the [CuL]2+ and [Cu(H-1L)]+ (L = L2, L2-Me, L2-Me3) complex cations, so that the peculiarities induced by the increase of N-methylation of ligands, the structural variable of ligands, can be highlighted. First, solution equilibria involving ligands and complexes were analyzed (potentiometry, NMR, UV-vis, ITC). Then, the appropriate conditions could be selected to prepare polyiodides based on the above complex cations. Single-crystal XRD analysis showed that the coordination of pyridinol units to two metal ions is a prime feature of these ligands, leading to polymeric coordination chains of general formula {[Cu(H-1L)]}nn+ (L = L2-Me, L2-Me3). In the presence of the I-/I2 couple, the polymerization tendency stops with the formation of [(CuL)(CuH-1L)]3+ (L = L2-Me, L2-Me3) dimers which are surrounded by polyiodide networks. Moreover, coordination of the pyridinol group to two metal ions transforms the surface charge of the ring from negative to markedly positive, generating a suitable environment for the assembly of polyiodide anions, while N-methylation shifts the directional control of the assembly from H-bonds to I···I interactions. In fact, an extended concatenation of iodine atoms occurs around the complex dimeric cations, the supramolecular I···I interactions become shorter and shorter, fading into stronger forces dominated by the orbital overlap, which is promising for effective electronic materials.
dc.language.iso eng
dc.relation.ispartof Inorganic Chemistry, 2022, vol. 61, num. 1, p. 368-383
dc.rights.uri info:eu-repo/semantics/openAccess
dc.source Martínez Camarena, Álvaro Savastano, Matteo Blasco Llopis, Salvador Delgado Pinar, Estefanía Giorgi, Claudia Bianchi, Antonio Garcia-España Monsonis, Enrique Bazzicalupi, Carla 2022 Assembly of Polyiodide Networks with Cu(II) Complexes of Pyridinol-Based Tetraaza Macrocycles Inorganic Chemistry 61 1 368 383
dc.subject Química
dc.subject Materials
dc.title Assembly of Polyiodide Networks with Cu(II) Complexes of Pyridinol-Based Tetraaza Macrocycles
dc.type info:eu-repo/semantics/article
dc.date.updated 2022-04-29T13:35:48Z
dc.identifier.doi https://doi.org/10.1021/acs.inorgchem.1c02967
dc.identifier.idgrec 152084

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