Syntheses, structures and properties of structurally characterised complexes of imide-based ligands

“…Regarding heterometallic frameworks, synthetic strategy using mixed 3d‐3d, 3d‐4f, 3d‐3d‐4f metals with distinct electron configurations, has been developed to construct MOFs with versatile organic ligands 5. In contrast, the construction of heterometallic MOFs based on s block and transition metals has been explored rarely 1a,6…”

Section: Introductionmentioning

confidence: 99%

Modeling the HCOOH/CO₂ Electrocatalytic Reaction: When Details Are Key

et al. 2015

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Our first principles simulations of the electrooxidation of formic acid over nickel identify the reorientation of the formate intermediate and the desorption of CO2 as the rate-limiting steps. Although they are not associated with an electron transfer, these barriers are strongly modified when the electrochemical potential is explicitly accounted for and when modeling the influence of the solvent. Hence, such a level of modeling is key to understand the kinetic limitations that penalize the reaction.

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“…1 The first structurally characterised imide complex was reported in 1976, with the imide formed accidentally, by hydrolysis of the initial triazine ligand. 2,3 By far the most commonly employed imide is the symmetric pyridine based ligand Hbpca (Fig.…”

Section: Introductionmentioning

confidence: 99%

“…Hence they have been used as building blocks to generate a large number of discrete and polymeric structural motifs. 1 The resulting 1-, 2-and 3-D assemblies are frequently mixed-valent or mixed-metal complexes, and have displayed a range of interesting properties including Single Molecule 35 Magnetism (SMM), 4,5 Single Chain Magnetism (SCM) 6,7 or luminescence, 8 as well as generating anion-exchangeable 9 or CO 2 vs N 2 selective 10 Metal Organic Frameworks (MOFs).…”

Section: Introductionmentioning

confidence: 99%

Pyrazine-imide complexes: reversible redox and MOF building blocks

2015

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The synthesis of the symmetric pyrazine imide ligand, N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, (Hdpzca) and five new first row transition metal complexes of it are reported: [M(II)(dpzca)(2)], M(II) = Fe, Cu, Zn; [Cu(II)(dpzca)(H(2)O)(2)]BF(4), [Cu(II)(dpzca)(H(2)O)(3)](2)SiF(6). The crystal structures of Hdpzca, [Co(II)(dpzca)(2)], [Cu(II)(dpzca)(2)], {[Co(III)(dpzca)(2)](BF(4))}(2)·5CH(3)CN and [Cu(II)(dpzca)(H(2)O)(3))](2)SiF(6)·2H(2)O were determined and reveal an orthogonal positioning of the 'spare' pyrazine nitrogen atoms and 'spare' pairs of imide oxygen atoms. The [M(II)(dpzca)(2)] complexes are therefore useful six-coordinate building blocks for producing larger supramolecular assemblies. Two examples of secondary assembly of [M(II)(dpzca)(2)] complexes, with M = Co and Ni, with silver nitrate gave single crystals; {[Co(III)(dpzca)(2)Ag](NO(3))(2)·2H(2)O}n and {([Ni(II)(dpzca)(2)Ag(I)(1/2)](1/2NO(3))(xH(2)O}n were structurally characterised. The redox processes of [M(II)(dpzca)(2)], with M(II) = Fe, Ni, Cu and Zn, are reported and, as seen for M(II) = Co, reversible metal- and ligand-based redox processes are observed, with E(m)(M(II)/M(III)) values 0.15-0.24 V higher than for the analogous complexes of Hpypzca (non-symmetric pyridine/pyrazine imide ligand), and 0.35-0.36 V higher than for the complexes of Hbpca (symmetric pyridine imide ligand).

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Syntheses, structures and properties of structurally characterised complexes of imide-based ligands

Cited by 23 publications

References 102 publications

A toolbox of building blocks, linkers and crystallisation methods used to generate single-chain magnets

A toolbox of building blocks, linkers and crystallisation methods used to generate single-chain magnets

Modeling the HCOOH/CO₂ Electrocatalytic Reaction: When Details Are Key

Pyrazine-imide complexes: reversible redox and MOF building blocks

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Syntheses, structures and properties of structurally characterised complexes of imide-based ligands

Cited by 23 publications

References 102 publications

A toolbox of building blocks, linkers and crystallisation methods used to generate single-chain magnets

A toolbox of building blocks, linkers and crystallisation methods used to generate single-chain magnets

Modeling the HCOOH/CO2 Electrocatalytic Reaction: When Details Are Key

Pyrazine-imide complexes: reversible redox and MOF building blocks

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Modeling the HCOOH/CO₂ Electrocatalytic Reaction: When Details Are Key