The Ligand 1,10-Phenanthroline-2,9-dicarbaldehyde Dioxime can Act Both as a Tridentate and as a Tetradentate Ligand − Synthesis, Characterization and Crystal Structures of its Transition Metal Complexes

Angeloff, Ariane; Daran, Jean‐Claude; Bernadou, Jean; Meunier, Bernard

doi:10.1002/1099-0682(200009)2000:9<1985::aid-ejic1985>3.3.co;2-b

Cited by 9 publications

(12 citation statements)

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“…All commercially available chemicals were of reagent grade and were used without further purification, except for 1,10phenanthroline-2,9-dicarbaldehyde dioxime (H 2 phendox or PDOX), which was synthesized according to a reported procedure ( Fig. S1 in the supporting information) (Angeloff et al, 2000;Chandler et al, 1981). IR spectra were recorded from KBr pellets in the 4000-400 cm À1 region using a Buck 500 IR spectrometer.…”

Section: Methodsmentioning

confidence: 99%

Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW₁₂O₄₀]⁴⁻: a synthetic, structural and computational investigation

et al. 2018

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As an extension of our continued interest in the preparation of inorganic–organic hybrids, we report the successful hydrothermal synthesis of sodium tris[triaqua(μ‐1,10‐phenanthroline‐2,9‐dicarboxylato)dysprosium(III)] silicododecatungstate dodecahydrate, {[DyNa(C14H6N2O4)3(H2O)9(SiW12O40)]·12H2O}n or Na[Dy(PDA)(H2O)3]3[SiW12O40]·12H2O (1), and sodium aqua tris[tetraaqua(μ‐4‐hydroxypyridine‐2,6‐dicarboxylato)praseodymium(III)] silicododecatungstate dodecahydrate, {[NaPr(C7H3NO5)3(H2O)13(SiW12O40)]·12H2O}n or Na(H2O)[Pr(pydc‐OH)(H2O)4]3[SiW12O40]·12H2O (2) (in which H2PDA is 1,10‐phenanthroline‐2,9‐dicarboxylic acid and H2pydc‐OH is 4‐hydroxypyridine‐2,6‐dicarboxylic acid or chelidamic acid). Both compounds have been characterized using elemental analysis, IR spectroscopy and X‐ray diffraction methods. Structural characterization by single‐crystal X‐ray diffraction reveals that these compounds consist of [SiW12O40]4− Keggin‐type polyoxometalates (POMs), where a single {W3O13} triad is decorated with a trinuclear Ln complex. Moreover, the decorated polyanions are involved in a series of intermolecular interactions, such as hydrogen bonds and anion–π interactions, resulting in three‐dimensional supramolecular architectures. Density functional theory (DFT) studies were conducted to support these intermolecular interactions in both 1 and 2, and have been rationalized using molecular electrostatic potential (MEP) surface calculations.

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Section: Methodsmentioning

confidence: 99%

Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW₁₂O₄₀]⁴⁻: a synthetic, structural and computational investigation

et al. 2018

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“…Some metal ion complexing properties of PDOX, which has two oximate donor groups at the 2 and 9 positions, have been reported. [128][129][130] The complexes of PDOX with small metal ions such as Zn(II) or Cu(II) have the ligand coordinating in a tridentate fashion (Scheme 9), with one oximate group left not coordinated. 128 With the large Pb(II) ion 129 PDOX acts as a tetradentate ligand, while with the Cd(II) ion, which is just below the 1.0 Å radius to be regarded as large, one structure has the PDOX binding in a tridentate fashion, and in another it is tetradentate.…”

Section: (C) Phen With Oximate Substituentsmentioning

confidence: 99%

The pyridyl group in ligand design for selective metal ion complexation and sensing

2013

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Factors in polypyridyl ligands that control their thermodynamic metal ion selectivity in aqueous solution, and their use in selective fluorescent sensing, are examined. Preorganization of polypyridyl ligands ranging from bidentate to tetradentate by bridging benzo groups, as are present in 1,10-phenanthroline (phen) compared to 2,2'-bipyridyl (bpy), is discussed. The role of solvation is considered in relation to the relative affinity of ligands containing pyridyl groups for divalent and trivalent metal ions in aqueous solution. The effects of steric clashes between H atoms on polypyridyl ligands in decreasing complex stability are evaluated, as well as the effect of chelate ring size on metal ion selectivity. Phen ligands with other donor groups present at the 2 and 9 positions, such as alcohols, amides, carboxylates, and oximes are discussed. The design of pyridyl-based ligands for the separation of Am(III) from lanthanide(III) ions is considered, as well as ligands for the removal of metal ions such as Cu(II) or Zn(II) in neurological diseases such as Alzheimer's. The design of pyridyl-based fluorescent sensors for selective sensing of metal ions is examined in terms of the role of spin-orbit coupling constants (ζ), paramagnetism, and steric effects in the development of selective fluorescent sensors that operate via chelation enhanced fluorescence (CHEF). It is concluded that for lighter metal ions with smaller ζ values such as Zn(II) and Ca(II), and to a lesser extent Cd(II), that the CHEF effect can be achieved with pyridyl-containing fluorophores that coordinate directly to the metal ion. The way in which steric effects can be used to decrease the CHEF effect in Zn(II) relative to Cd(II) to enable selective sensing of the latter is analyzed. For heavier metal ions such as Hg(II) and Pb(II), because of their large ζ values which quench fluorescence, it is concluded that the fluorophore should be tethered to the metal-binding part of the sensor, and prevented from binding to the metal ion by steric and electronic factors. How Hg(II) can quench the CHEF effect by π-contact with fluorophores such as the anthracenyl group, which at first sight might not seem able to bond with metal ions, is examined.

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“…= 4, 5, or 6) of a symmetric N,S mixed ligand (L) closely related to NSN(Qui [14] Search (c) returned about 20 entries, but only 11 of these show an aliphatic amine donor atom like 3. In the reported structures, the Zn-N py , Zn-N ali (N py = pyridine nitrogen, N ali = aliphatic amine nitrogen), and Zn-Cl distances vary, respectively, in the ranges 2.039 [28] -2.511, [28] 2.129 [29] -2.464, [30] and 2.220 [30] -2.345 [29] Å. In 3, the Zn-N py bonds are 2.124(3), 2.156(3) Å, Zn-N ali is 2.234(3) Å, and the ZnCl distances are 2.252(1) and 2.343(1) Å, respectively.…”

Section: X-ray Crystal Structurementioning

confidence: 99%

Synthesis, Stability Constant Determination, and Structural Study of Some Complexes of a Zinc Triad Containing Pyridyl‐amine‐quinoline and Pyridyl‐thio‐quinoline

et al. 2007

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Keywords: Zinc / Quinoline-based ligands / Fluorescence / Formation constantsThe potentially fluorescent and terdentate ligands containing nitrogen or sulfur as coordinating atom were synthesized and used in the formation of perchlorate or chloride complexes of the metals of the Zn triad. The reaction of the ligands with metal perchlorate salts yields the corresponding bis-chelate derivatives, whereas the same ligands react with metal chloride salts to give monochelate complexes. All of these complexes undergo NMR-scale fast fluxional rearrangement in solution. Some structural X-ray diffractometric studies were also performed and the ensuing data confirm the surmised structures and the solution rearrangement in the case of monochelate substrates and of one Hg derivative, respec-

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The Ligand 1,10-Phenanthroline-2,9-dicarbaldehyde Dioxime can Act Both as a Tridentate and as a Tetradentate Ligand − Synthesis, Characterization and Crystal Structures of its Transition Metal Complexes

Cited by 9 publications

References 0 publications

Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW₁₂O₄₀]⁴⁻: a synthetic, structural and computational investigation

Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW₁₂O₄₀]⁴⁻: a synthetic, structural and computational investigation

The pyridyl group in ligand design for selective metal ion complexation and sensing

Synthesis, Stability Constant Determination, and Structural Study of Some Complexes of a Zinc Triad Containing Pyridyl‐amine‐quinoline and Pyridyl‐thio‐quinoline

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The Ligand 1,10-Phenanthroline-2,9-dicarbaldehyde Dioxime can Act Both as a Tridentate and as a Tetradentate Ligand − Synthesis, Characterization and Crystal Structures of its Transition Metal Complexes

Cited by 9 publications

References 0 publications

Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW12O40]4−: a synthetic, structural and computational investigation

Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW12O40]4−: a synthetic, structural and computational investigation

The pyridyl group in ligand design for selective metal ion complexation and sensing

Synthesis, Stability Constant Determination, and Structural Study of Some Complexes of a Zinc Triad Containing Pyridyl‐amine‐quinoline and Pyridyl‐thio‐quinoline

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Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW₁₂O₄₀]⁴⁻: a synthetic, structural and computational investigation

Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW₁₂O₄₀]⁴⁻: a synthetic, structural and computational investigation