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

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.

SUBMITTER: Martinez-Camarena A

PROVIDER: S-EPMC8753606 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:New Co(II), Ni(II), and Cu(II) complexes were synthesized with the Schiff base ligand obtained by the condensation of sulfathiazole with salicylaldehyde. Their characterization was performed by elemental analysis, molar conductance, spectroscopic techniques (IR, diffuse reflectance and UV-Vis-NIR), magnetic moments, thermal analysis, and calorimetry (thermogravimetry/derivative thermogravimetry/differential scanning calorimetry), while their morphological and crystal systems were explained on the basis of powder X-ray diffraction results. The IR data indicated that the Schiff base ligand is tridentate coordinated to the metallic ion with two N atoms from azomethine group and thiazole ring and one O atom from phenolic group. The composition of the complexes was found to be of the [ML2]∙nH2O (M = Co, n = 1.5 (1); M = Ni, n = 1 (2); M = Cu, n = 4.5 (3)) type, having an octahedral geometry for the Co(II) and Ni(II) complexes and a tetragonally distorted octahedral geometry for the Cu(II) complex. The presence of lattice water molecules was confirmed by thermal analysis. XRD analysis evidenced the polycrystalline nature of the powders, with a monoclinic structure. The unit cell volume of the complexes was found to increase in the order of (2) < (1) < (3). SEM evidenced hard agglomerates with micrometric-range sizes for all the investigated samples (ligand and complexes). EDS analysis showed that the N:S and N:M atomic ratios were close to the theoretical ones (1.5 and 6.0, respectively). The geometric and electronic structures of the Schiff base ligand 4-((2-hydroxybenzylidene) amino)-N-(thiazol-2-yl) benzenesulfonamide (HL) was computationally investigated by the density functional theory (DFT) method. The predictive molecular properties of the chemical reactivity of the HL and Cu(II) complex were determined by a DFT calculation. The Schiff base and its metal complexes were tested against some bacterial strains (Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus subtilis). The results indicated that the antibacterial activity of all metal complexes is better than that of the Schiff base.

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

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