Hydrothermal Synthesis and Characterization of 2D M(II)-Quinate (M = Co,Zn) Metal−Organic Lattice Assemblies: Solid-State Solution Structure Correlation in M(II)-Hydroxycarboxylate Systems

Menelaou, Melita; Konstantopai, A.; Lalioti, Nikolia; Raptopoulou, Catherine P.; Psycharis, Vassilis; Terzis, Aris; Mateescu, C.; Tsarhopoulos, K.; Rigas, Pantelis G.; Salifoglou, Athanasios

doi:10.1021/ic1013945

Cited by 13 publications

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References 69 publications

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“…Noncentrosymmetric coordination polymers (CPs) have attracted considerable attention due to their useful electrical and optical properties . Naturally occurring chiral α-hydroxy acids are useful bridging blocks for the construction of noncentrosymmetric CPs and metal complexes because these molecules are readily available without any need for complicated synthetic procedures. − Mandelic acid, which consists of a hydrophobic phenyl group and hydrophilic hydroxyl and carboxyl groups at a chiral methine carbon (Figure a), possesses suitable characters to synthesize chiral CPs. Owing to these functional groups, the mandelate ligand forms inter- and intramolecular interactions through aromatic interactions and hydrogen bonds to stabilize the highly ordered self-assembled structure of CPs. − ,− Thus, the synthetic route to noncentrosymmetric metal–mandelate CPs has been studied through the alteration of auxiliary ligands. − , …”

Section: Introductionmentioning

confidence: 99%

Non-Centrosymmetric Coordination Polymer with a Highly Hindered Octahedral Copper Center Bridged by Mandelate

et al. 2012

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A novel chiral coordination polymer, [Cu(C(6)H(5)CH(OH)COO)(μ-C(6)H(5)CH(OH)COO)] (1-L and 1-D), was synthesized through a reaction of copper acetate with L-mandelic acid at room temperature. Although previously reported copper mandelate prepared by hydrothermal reaction was a centrosymmetric coordination polymer because of the racemization of mandelic acid, the current coordination polymer shows noncentrosymmetry and a completely different structure from that previously reported. The X-ray crystallography for 1-L revealed that the copper center of the compound showed a highly distorted octahedral structure bridged by a chiral mandelate ligand in the unusual coordination mode to construct a one-dimensional (1D) zigzag chain structure. These 1D chains interdigitated each other to give a layered structure as a result of the formation of multiple aromatic interactions and hydrogen bonds between hydroxyl and carboxylate moieties at mandelate ligands. The coordination polymer 1-L belongs to the noncentrosymmetric space group of C2 to show piezoelectric properties and second harmonic generation (SHG) activity.

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Section: Introductionmentioning

confidence: 99%

Non-Centrosymmetric Coordination Polymer with a Highly Hindered Octahedral Copper Center Bridged by Mandelate

et al. 2012

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“…The quinato ligand plays the role of an efficient metal ion chelator (mode I and mode II in Scheme ), capable of effectively formulating the coordination environment around iron ions in 1 and 2 . This coordination ability has also been observed in the case of (di-, multi)valent transition metal ions, with representative examples being K[Co(C 7 H 11 O 6 ) 3 ]·3CH 3 CH 2 OH ( 11 ), [Co(C 7 H 11 O 6 ) 2 (H 2 O) 2 ]·3H 2 O ( 12 ), Na[Ni(C 7 H 11 O 6 ) 3 ]·2.75H 2 O ( 13 ), [Cu(C 7 H 10 O 6 )(H 2 O)] 2 (H 2 O) 2 ( 14 ), {[CuCl(C 7 H 11 O 6 )(H 2 O)]·H 2 O} n ( 15 ), [Zn(C 7 H 11 O 6 ) 2 ] ( 16 ), [Cd(C 7 H 11 O 6 ) 2 ]·H 2 O ( 17 ), [Co 2 (C 7 H 11 O 6 ) 4 ] n · n H 2 O·( 18 ), [Zn 3 (C 7 H 11 O 6 ) 6 ] n · n H 2 O ( 19 ), and [Pt(C 6 H 14 N 2 )(C 7 H 10 O 6 )] ( 20 ) . Only three mononuclear Fe(III)–quinato species have been reported: (Cat)[Fe(C 7 H 11 O 6 ) 3 ]·(OH)· y H 2 O where (Cat)/ y = NH 4 + /0 ( 21 ), K + /3 ( 22 ), Na + /8 ( 23 ), respectively …”

Section: Methodsmentioning

confidence: 74%

“…Thus, each hydroxycarboxylato binder is coordinated to two distinct iron sites in 1 and 2 . Involvement of one of the terminal alcoholic moieties in the formation of dinuclear species in binary systems has been previously observed, leading to a 1:2 metal-to-ligand ratio compounds in Mn(II), Co(II), and trinuclear species in Zn(II); thus, suggesting that the presence of the terminal alcohols in d -(-)-quinic acid can be a key factor in the synthesis of polynuclear clusters either from binary or ternary systems, with structural differences and/or similarities compared to the aforementioned characterized materials.…”

Section: Discussionmentioning

confidence: 99%

Heptanuclear Antiferromagnetic Fe(III)–d-(-)-Quinato Assemblies with an S = 3/2 Ground State—pH-Specific Synthetic Chemistry, Spectroscopic, Structural, and Magnetic Susceptibility Studies

et al. 2013

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Iron is an essential metal ion with numerous roles in biological systems and advanced abiotic materials. D-(-)-quinic acid is a cellular metal ion chelator, capable of promoting reactions with metal M(II,III) ions under pH-specific conditions. In an effort to comprehend the chemical reactivity of well-defined forms of Fe(III)/Fe(II) toward α-hydroxycarboxylic acids, pH-specific reactions of: (a) [Fe3O(CH3COO)6(H2O)3]·(NO3)·4H2O with D-(-)-quinic acid in a molar ratio 1:3 at pH 2.5 and (b) Mohr's salt with D-(-)-quinic acid in a molar ratio 1:3 at pH 7.5, respectively, led to the isolation of the first two heptanuclear Fe(III)-quinato complexes, [Fe7O3(OH)3(C7H10O6)6]·20.5H2O (1) and (NH4)[Fe7(OH)6(C7H10O6)6]·(SO4)2·18H2O (2). Compounds 1 and 2 were characterized by analytical, spectroscopic (UV-vis, FT-IR, EPR, and Mössbauer) techniques, CV, TGA-DTG, and magnetic susceptibility measurements. The X-ray structures of 1 and 2 reveal heptanuclear assemblies of six Fe(III) ions bound by six doubly deprotonated quinates and one Fe(III) ion bound by oxido- and hydroxido-bridges (1), and hydroxido-bridges (2), all in an octahedral fashion. Mössbauer spectroscopy on 1 and 2 suggests the presence of Fe(III) ions in an all-oxygen environment. EPR measurements indicate that 1 and 2 retain their structure in solution, while magnetic measurements reveal an overall antiferromagnetic behavior with a ground state S = 3/2. The collective physicochemical properties of 1 and 2 suggest that the (a) nature of the ligand, (b) precursor form of iron, (c) pH, and (d) molecular stoichiometry are key factors influencing the chemical reactivity of the binary Fe(II,III)-hydroxycarboxylato systems, their aqueous speciation, and ultimately through variably emerging hydrogen bonding interactions, the assembly of multinuclear Fe(III)-hydroxycarboxylato clusters with distinct lattice architectures of specific dimensionality (2D-3D) and magnetic signature.

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“…Zinc is an important trace metal ion in all living organisms, influencing nutrition [1], gene expression and cell division [2,3], and even in plant metabolic processes [4]. It has a wide range of applications, including batteries [5], alloys [6], dye-casting [7], dental materials [8], Zn-doped ferrites [9,10], etc.…”

Section: Introductionmentioning

confidence: 99%

Solid and solution study of tetranuclear zinc citrates with N-donor chelates

Zhou

Xiao

et al. 2014

Journal of Coordination Chemistry

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300 350 400 450 500 0 200 400 600 800 Intensity (a.u.) (nm) 1 in CH 3 OH 1 solid powder 2 in CH 3 OH 2 solid powder Two tetranuclear zinc(II) citrates with N-heterocycle ligand, [Zn 4 (Hcit) 2 (phen) 4 (H 2 O) 4 ]·2NO 3 ·10H 2 O (1) and [Zn 4 (Hcit) 2 (bpy) 4 (H 2 O) 6 ]·2NO 3 ·12H 2 O (2) (H 4 cit = citric acid, phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine), were synthesized from aqueous solution and characterized by Infrared, Powder X-ray diffraction, fluorescence spectra and X-ray structural analyses. 1 and 2 show strong fluorescent emission in dilute solution and solid state. Tetranuclear zinc(II) citrates with N-heterocycle ligand, [Zn 4 (Hcit) 2 (phen) 4 (H 2 O) 4 ]·2NO 3 ·10H 2 O (1) and [Zn 4 (Hcit) 2 (bpy) 4 (H 2 O) 6 ]·2NO 3 ·12H 2 O (2) (H 4 cit = citric acid, phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine), were synthesized from aqueous solution and characterized by Infrared, Powder X-ray diffraction, fluorescence spectra, and X-ray structural analyses. Complexes 1 and 2 are centrosymmetric tetranuclear species with two crystallographically independent Zn(II) ions, which display different coordination geometries, while the citrate ligand shows similar coordination modes and bridges three different Zn ions. In 1, the Zn1 is five-coordinate by three oxygens from two citrates and two nitrogens from phen. There exist weak interactions between Zn1 and O4a atom of β-carboxy group of citrate (Zn1⋯O4a = 2.895 Å). Zn2 is six-coordinate by two oxygens from one citrate, two nitrogens from phen, and two water molecules. Zn1 and Zn2 are bridged by one citrate to form a dinuclear unit, which is further extended to a tetranuclear unit. In 2, two citrates bridge two pairs of symmetry-related Zn(II) ions into a tetranuclear unit. The structural analyses of 1 and 2 indicate that different tetranuclear species are caused by arrangement of citrates with different steric *Corresponding authors.hindrance of N-chelates. 1 H and 13 C NMR spectra indicate that 2 remains coordinated in D 2 O. Moreover, both 1 and 2 show strong fluorescent emission in dilute solution and solid state.

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Hydrothermal Synthesis and Characterization of 2D M(II)-Quinate (M = Co,Zn) Metal−Organic Lattice Assemblies: Solid-State Solution Structure Correlation in M(II)-Hydroxycarboxylate Systems

Cited by 13 publications

References 69 publications

Non-Centrosymmetric Coordination Polymer with a Highly Hindered Octahedral Copper Center Bridged by Mandelate

Non-Centrosymmetric Coordination Polymer with a Highly Hindered Octahedral Copper Center Bridged by Mandelate

Heptanuclear Antiferromagnetic Fe(III)–d-(-)-Quinato Assemblies with an S = 3/2 Ground State—pH-Specific Synthetic Chemistry, Spectroscopic, Structural, and Magnetic Susceptibility Studies

Solid and solution study of tetranuclear zinc citrates with N-donor chelates

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