Syntheses, structures of manganese/cadmium/ferrous complexes and magnetic property of manganese complex with the ligand 5-hydroxynicotinic acid

doi:10.1016/j.inoche.2010.10.026

Inorganic Chemistry Communications

Volume 14, Issue 1, January 2011, Pages 217-220

https://doi.org/10.1016/j.inoche.2010.10.026 Get rights and content

Abstract

Three new coordination polymers, namely [Mn₂(5-phenoxonicotinato)₂] (1), [Cd₂(5-phenoxonicotinato)₂] (2), and [Fe₂(5-phenoxonicotinato)₂] (3), have been synthesized under hydrothermal conditions and characterized structurally by single-crystal X-ray diffraction. The structure of compound 1 can be described as a 3D metal-organic framework which is constructed by two kinds of crystallographical unique Mn cations and one kind of μ₆-5-phenoxonicotinato bridging ligand, featuring a 6,6-connected {3·4¹⁰·6⁴}{4⁹·6⁶} topology structure. Taking Cd and Fe ions in place of Mn ions respectively, two new compounds 2 and 3 are successfully obtained which are isostructural with 1. In addition, the magnetic property of compound 1 is investigated in detail.

Graphical abstract

Three new 3D coordination polymers, [M(II)₂(5-phenoxonicotinato)₂]_n, (M = Mn 1, M = Cd 2, and M = Fe 3) constructed by two kinds of structurally independent metal ions with one kind of μ₆-5-phenoxonicotinato bridge are isostructural and exhibit a novel 6,6-connected {3·4¹⁰·6⁴}{4⁹·6⁶} topology structure. The study on magnetic property of compound 1 reveals that antiferromagnetic interactions exist between the neighboring Mn(II) ions.

Research Highlights

► 5-hydroxynicotinic acid can coordinate with Mn(II)/Cd(II)/Fe(II) ions directly forming 3D MOFs. ► The three 3D MOFs exhibit a novel 6,6-connected {3·4¹⁰·6⁴} {4⁹·6⁶} topology structure. ► The stratagem for synthesizing the three 3D MOFs simplifies crystal engineering. ► Compound 1 reveals antiferromagnetic interactions between the neighboring Mn(II) ions.

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Synthesis, structural characterization and application of a 2D coordination polymer of Mn-terephthalate as a heterogeneous catalyst for olefin oxidation
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Citation Excerpt :
It is widespread that the careful selection of the bridging ligands is one of the major factors for the synthesis of the CPs with novel structures. As a type of multidentate ligands, carboxylate derived ligands play an essential role in coordination chemistry and have attracted great attention because they can adopt various binding modes (i.e. monodentate, chelating, bridging) and have been widely manipulated to create polynuclear metal complexes with intriguing structural motifs [28–31]. CPs based on carboxylate ligands are especially suitable for catalysis, leading to a new generation of solid catalysts with uniform catalytic sites and open channel structures for different catalytic reactions [32,33].
A metal–organic coordination polymer of [Mn₃(1,4-benzenedicarboxylate)₃(DMF)₄] ([Mn₃(BDC)₃(DMF)₄]_n) was synthesized and characterized by IR spectra, elemental analysis (CHN), thermal gravimetric analysis (TGA) and single crystal X-ray diffraction analysis. The structure of [Mn₃(BDC)₃(DMF)₄]_n is a 2D-periodic framework based on Mn(II)-terephthalate secondary building units (SBUs). The catalytic oxidation of various olefins was effectively carried out with [Mn₃(BDC)₃(DMF)₄]_n. Moreover, the influence of key reaction parameters, including the solvents, reaction temperatures and nature of oxidant were studied. The optimized conditions were achieved by TBHP as the efficient oxidant in 1,2-dichloroethane solvent at 75 °C. Finally, this catalyst was used for four cycles efficiently without a significant loss of yield.
Two- and three-dimensional lanthanide metal-organic frameworks with hydroxyl-functionalized nicotinic acid and oxalate ligands
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A series of LMOFs, consisting of three groups of isostructural compounds, [Ln(3-H-5-phenoxonicotinato)(ox)(H₂O)₂]_n 1 (Ln = La(1a), Pr(1b), Nd(1c), 5-Hydroxynicotinic acid = C₆H₅NO₃, ox = C₂O₄^2 −), {[Ln(3-H-5-hydroxynicotinato)(ox)_1.5(H₂O)]⋅H₂O}_n 2 (Ln = Sm(2a), Gd(2b), Tb(2c), and {[Ln(3-H-5-phenoxonicotinato)(ox)(H₂O)]⋅H₂O}_n 3 (Ln = Dy(3a), Er(3b), have been hydrothermally synthesized and structurally determined by X-ray diffraction analyses. Compounds in group 1 are constructed by mixed μ₃-3-H-5-phenoxonicotinato and oxalate bridging ligands and Ln^3 + ions, exhibiting a 3D covalent network with empty 1D microchannels, featuring a 3,5-connected topology symbol of {4²⋅ 6⁵⋅ 8³}⋅{4²⋅ 6}. Compounds in group 2 present a brick-well-liked 2D network generated by both metal ions and oxalate groups at a side-by-side way. Compounds in group 3 are isotopological to those in group 1, accompanying 1D microchannels being occupied by coordinated water molecules. Antiferromagnetic interactions between praseodymium metal centers are observed from the magnetic susceptibility of compound 1b. In addition, luminescence measurements indicate that the terbium complex 2c is a strong green luminescence emitter.
Poly[tetraaqua(5-hydroxypyridin-1-ium-3-carboxylato-κO 3)tris(μ-oxalato-κ4 O 1,O 2:O 1′,O 2′)dieuropium(III)]
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2011, Jiegou Huaxue

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Inorganic Chemistry Communications

Abstract

Graphical abstract

Research Highlights

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Cited by (5)

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Two- and three-dimensional lanthanide metal-organic frameworks with hydroxyl-functionalized nicotinic acid and oxalate ligands

Poly[tetraaqua(5-hydroxypyridin-1-ium-3-carboxylato-κO <sup>3</sup>)tris(μ-oxalato-κ<sup>4</sup> O <sup>1</sup>,O <sup>2</sup>:O <sup>1′</sup>,O <sup>2′</sup>)dieuropium(III)]

Synthesis, crystal structure and magnetic properties of a coordination polymer [Ni(cpna)(bpy)(H<inf>2</inf>O)]<inf>n</inf>

Hydrothermal synthesis and crystal structure of a 2D zinc(II) coordination polymer with 5-hydroxynicotinic acid