Linked Nickel Metallacrowns from a Phosphonate/2-Pyridyloximate Blend of Ligands: Structure and Magnetic Properties

Escuer, Albert; Mayans, Júlia; Font-Bardı́a, Mercè

doi:10.1021/acs.inorgchem.6b00103

Cited by 11 publications

(5 citation statements)

References 46 publications

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“…The most salient property of these L1–L4 ligands is probably the ability of their neutral (not-protonated) forms to form stable complexes with hydroxide (OH − ) anions in water. Actually, as far as we know, these are the first reported cases of non-covalent binding of hydroxide anions in water with metal-free synthetic receptors, even if examples of OH − anions interacting with electron-poor aromatic groups in the solid state can be found in published crystal structures [25,26,27,28,29,30,31,32,33,34,35,36,37,38,39]. In only a few of them, the existence of anion–π interactions was noted [31].…”

Section: Resultsmentioning

confidence: 99%

Solid State and Solution Study on the Formation of Inorganic Anion Complexes with a Series of Tetrazine-Based Ligands

et al. 2019

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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.

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Section: Resultsmentioning

confidence: 99%

Solid State and Solution Study on the Formation of Inorganic Anion Complexes with a Series of Tetrazine-Based Ligands

et al. 2019

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“…Meanwhile, the two unique µ 3 -PhPO 3 2− bridges are the crucial factor for proton transformation during the catalytic process. In addition, N atoms on the oxime group could serve as an edge base, which can donate σ electrons to the Ni metal centers while obtaining π electrons through π back-bonding to modulate the electronic structure of the metal centers [52][53][54][55][56][57][58][59][60][61][62]. The two kinds of ligands could highly boost the electrocatalytic performance of complex 1.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Water Oxidation and CO2 Reduction with a Nickel Molecular Catalyst

Jian,

Lu,

Zheng

et al. 2024

Molecules

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Mimicking the photosynthesis of green plants to combine water oxidation with CO2 reduction is of great significance for solving energy and environmental crises. In this context, a trinuclear nickel complex, [NiII3(paoH)6(PhPO3)2]·2ClO4 (1), with a novel structure has been constructed with PhPO32− (phenylphosphonate) and paoH (2-pyridine formaldehyde oxime) ligands and possesses a reflection symmetry with a mirror plane revealed by single-crystal X-ray diffraction. Bulk electrocatalysis demonstrates that complex 1 can homogeneously catalyze water oxidation and CO2 reduction simultaneously. It can catalyze water oxidation at a near-neutral condition of pH = 7.45 with a high TOF of 12.2 s−1, and the Faraday efficiency is as high as 95%. Meanwhile, it also exhibits high electrocatalytic activity for CO2 reduction towards CO with a TOF of 7.84 s−1 in DMF solution. The excellent electrocatalytic performance of the water oxidation and CO2 reduction of complex 1 could be attributed to the two unique µ3-PhPO32− bridges as the crucial factor for stabilizing the trinuclear molecule as well as the proton transformation during the catalytic process, while the oxime groups modulate the electronic structure of the metal centers via π back-bonding. Therefore, apart from the cooperation effect of the three Ni centers for catalysis, simultaneously, the two kinds of ligands in complex 1 can also synergistically coordinate the central metal, thereby significantly promoting its catalytic performance. Complex 1 represents the first nickel molecular electrocatalyst for both water oxidation and CO2 reduction. The findings in this work open an avenue for designing efficient molecular electrocatalysts with peculiar ligands.

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“…Due to the large interest in this field, several supramolecular complexes, such as complexes of nickel(II),, copper(II) and many other transition metals, were described in the last few years. An overview of various structural types of metallacrowns was published by Pecoraro and co‐workers in 2007 and its potential applications in catalysis, adsorption, molecular magnetism and luminescence were summarized by Ostrowska et al Moreover, it is worth mentioning that self‐assembled SCCs as well as organometallic metallacrowns can act as receptors for small ions, as pointed out by K. Severin…”

Section: Introductionmentioning

confidence: 99%

Alkali‐Metal‐Templated Self‐Assembly of Nickel(II) [12‐MC‐3] Metallacoronates Based on Bis(pyrazol‐1‐yl)acetato Ligands

et al. 2018

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The syntheses and structures of four new bis(pyrazol-1-yl)acetate-or bis(3,5-dimethylpyrazol-1-yl)acetate-based bisligand nickel(II) complexes [Ni(bdmpzmp) 2 ] (1), [Ni-(bdmpzpen) 2 ] (2), [Ni(bdmpza) 2 ] (3), and [Ni(bpza) 2 ] (4) are described. The results of single crystal structure determinations reveal for all four complexes κ 3 -coordination of the scorpionate ligands. The sterically hindered bis(3,5-di-tert-butyl-pyrazol-1yl)acetateto (bdtbpza) ligand allows the synthesis of the nickel(II) chlorido complex [Ni(bdtbpza)Cl] (5). Furthermore, controlled formation of a novel trinuclear linear complex [Ni(bdmpza) 2 {Ni(acac)(bdmpza)} 2 ] (6) [bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate] by a self-assembling reaction and alkali metal-mediated template syntheses of [Na{Ni(acac)- [a]

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Linked Nickel Metallacrowns from a Phosphonate/2-Pyridyloximate Blend of Ligands: Structure and Magnetic Properties

Cited by 11 publications

References 46 publications

Solid State and Solution Study on the Formation of Inorganic Anion Complexes with a Series of Tetrazine-Based Ligands

Solid State and Solution Study on the Formation of Inorganic Anion Complexes with a Series of Tetrazine-Based Ligands

Electrochemical Water Oxidation and CO2 Reduction with a Nickel Molecular Catalyst

Alkali‐Metal‐Templated Self‐Assembly of Nickel(II) [12‐MC‐3] Metallacoronates Based on Bis(pyrazol‐1‐yl)acetato Ligands

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