Synthesis, structure and magnetic studies of two-dimensional network of Cu(II) polymer using malonate and 4,4′-azobispyridine ligands

Li, Baolong; Wang, Xin‐Yi; Zhang, Yuping; Gao, Song; Zhang, Yong

doi:10.1016/j.ica.2005.04.023

Cited by 16 publications

(5 citation statements)

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“…The possibility of π···π and C–H/π type intermolecular interactions between the azpy ligand and the alkyl or aryl groups of the substituted malonate could play a significant structural role and even modify the final network . Only one complex combining the malonate and the azpy ligand of formula [Cu(mal)(H 2 O)(azpy) 1/2 ]·H 2 O has been previously reported . Its structure consists of syn – anti malonate-bridged copper(II) chains, which are linked through azpy to build a two-dimensional network where ferro- (intrachain) and antiferromagnetic (interchain) interactions coexist.…”

Section: Introductionmentioning

confidence: 99%

Pillaring Role of 4,4′-Azobis(pyridine) in Substituted Malonate-Containing Manganese(II) Complexes: Syntheses, Crystal Structures, and Magnetic Properties

Déniz

Hernández-Rodríguez

Pasán

et al. 2012

Crystal Growth & Design

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Six new manganese(II) complexes of formulas [Mn2(Rmal)2(H2O)2(azpy)] n (1–3), [Mn(Phmal)(H2O)(azpy)] n (4), [Mn2(Et2mal)2(H2O)4(azpy)2] n (5), and [Mn(Bzmal)(H2O)3(azpy)] (6) [azpy = 4,4′-azobispyridine (1–6), Rmal = methylmalonate (Memal) (1), dimethylmalonate (Me2mal) (2), and butylmalonate (Butmal) (3), Phmal = phenylmalonate (4), Et2mal = diethylmalonate (5), and Bzmal = benzylmalonate (6)] were synthesized and structurally characterized by single-crystal X-ray diffraction. Complexes 1–3 are three-dimensional compounds whose structure consists of corrugated layers of manganese(II) linked through syn–anti carboxylate (Rmal) bridges, which are pillared through the bis-monodentate azpy molecule. Complex 4 has a layered structure of manganese(II) ions connected by carboxylate (Phmal) bridges in the syn–anti coordination mode as in 1–3, the azpy group acting here as a terminally bound monodentate ligand. The structure of 5 consists of Et2mal–Mn(II) neutral chains linked through the azpy ligand, giving rise to a complex three-dimensional network. Complex 6 is constituted by neutral [Mn(Bzmal)(H2O)3(azpy)] mononuclear units, which are interlinked through O–H···O, O–H···N, and π–π type intermolecular interactions to afford a three-dimensional supramolecular structure. The topological analysis of these crystallographic structures shows the occurrence of four different nets: a (3,4)-connected InS-type (1–3), a binodal layered hcb (4), a uninodal CdS-type (5), and a (4,5)-connected tcs topology (6). The magnetic properties of 1–5 were investigated in the 2.0–300 K temperature range. Overall antiferromagnetic behavior occurs in 1–4 with susceptibility maxima in the range 2.8–5.5 K, the exchange pathway being provided by the syn–anti carboxylate (substituted malonate) bridge [manganese–manganese separation in the range 5.4365(3)–5.5274(1) Å]. Very weak antiferromagnetic interactions are observed in 5 through the trans-bis-monodentate Et2mal ligand, the intrachain manganese–manganese separation being 7.328(3) Å. The much larger manganese–manganese separation through the bis-monodentate azpy ligand in 1–5 (values greater than 13.5 Å) accounts for the lack of any significant magnetic interaction though this extended bridge.

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Section: Introductionmentioning

confidence: 99%

Pillaring Role of 4,4′-Azobis(pyridine) in Substituted Malonate-Containing Manganese(II) Complexes: Syntheses, Crystal Structures, and Magnetic Properties

Déniz

Hernández-Rodríguez

Pasán

et al. 2012

Crystal Growth & Design

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“…The pyridyl moieties represent the coordination mode A (Chart ), and the nitrogen atoms of the azo bridge the coordination mode B (Chart ). The coordination mode A has been used to construct a variety of coordination geometries depending on the metal center. , In such a way, multinuclear complexes (such as dimers, squares, and rectangles), ,,− molecular frameworks (for instance brick stone, herringbone, or wave-like motifs), ,,− and coordination polymers ,− become available. In contrast, the coordination mode B is less common .…”

Section: Introductionmentioning

confidence: 99%

“…The coordination mode A has been used to construct a variety of coordination geometries depending on the metal center. 42,43 In such a way, multinuclear complexes (such as dimers, squares, and rectangles), 32,41,[44][45][46][47] molecular frameworks (for instance brick stone, herringbone, or wave-like motifs), 26,29,[48][49][50][51][52][53][54][55] and coordination polymers 54,[56][57][58] become available. In contrast, the coor-dination mode B is less common.…”

Section: Introductionmentioning

confidence: 99%

Reactions of Low-Valent Titanocene(II) Fragments with trans-4,4′-Azobispyridine (RN═NR, R = C₅H₄N): Formation of Tetranuclear Molecular Squares by trans−cis Isomerization

et al. 2009

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The reactions of the low-valent titanocene sources [Cp* 2 Ti(η 2 -C 2 (TMS) 2 )] (2) and [tBuCp 2 Ti(η 2 -C 2 -(TMS) 2 )] (3) with trans-4,4′-azobispyridine (8) leads to novel supramolecular squares [(Cp* 2 Ti) 4 (µ 2 -N,N′;η 2 -N,N′-C 10 H 8 N 4 ) 2 ] (10) and [(tBuCp 2 Ti) 4 (µ 2 -N,N′;η 2 -N,N′-C 10 H 8 N 4 ) 2 ] (11). These complexes consist of four bent-titanocene corner units and two azo ligands 8. Within this self-assembly process the azo ligands experience a conformational rearrangement from trans to cis. The titanocene moieties are embedded with two different N-donor environments, provided by the pyridyl rings and the azo functionality of 8. Single-crystal X-ray analyses of the tetranuclear compounds 10 and 11 revealed the structural features of these molecular polygons. Exclusively cis-configurated azopyridine units are detected in 10 and 11. Comparison of bond lengths and angles in coordinated and free ligands shows a reduced state of the bridging ligands in the low-valent titanium complexes 10 and 11. In such a way, the N azo -N azo distances are elongated from 1.251(2) Å in 8 to av 1.405(3) Å (10) and 1.434(3) Å ( 11), respectively. The syntheses and attributes of these novel compounds are discussed. From the reaction of [Cp 2 Ti(η 2 -C 2 (TMS) 2 )] (1) with 8, 1,2-bis(4-pyridyl)hydrazine ( 13) was isolated and fully characterized as a subsequent product.

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“…The presence of the azo group makes this ligand a promising conductor through electronic coupling, while the possibility of protonation and/or isomerization, such as those studied in ferrocenylazobenzenes [3], is important in the design of ''molecular switches". Moreover, the p-p stacking effects caused by the planar structure of this ligand lead to interesting supramolecular structures with potential applications in hostguest chemistry [4][5][6][7]. On the other hand, polypyridyl ruthenium(II) complexes have been extensively studied in association with fundamental energy and electron transfer processes relevant in the design of solar energy conversion schemes used, for example, in dye-sensitized solar cells [8].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, spectroscopic and electrochemical characterization and molecular structure of polypyridyl ruthenium complexes containing 4,4′-azobis(pyridine)

Pourrieux¹,

Fagalde²,

Katz³

et al. 2008

Polyhedron

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Synthesis, structure and magnetic studies of two-dimensional network of Cu(II) polymer using malonate and 4,4′-azobispyridine ligands

Cited by 16 publications

References 57 publications

Pillaring Role of 4,4′-Azobis(pyridine) in Substituted Malonate-Containing Manganese(II) Complexes: Syntheses, Crystal Structures, and Magnetic Properties

Pillaring Role of 4,4′-Azobis(pyridine) in Substituted Malonate-Containing Manganese(II) Complexes: Syntheses, Crystal Structures, and Magnetic Properties

Reactions of Low-Valent Titanocene(II) Fragments with trans-4,4′-Azobispyridine (RN═NR, R = C₅H₄N): Formation of Tetranuclear Molecular Squares by trans−cis Isomerization

Synthesis, spectroscopic and electrochemical characterization and molecular structure of polypyridyl ruthenium complexes containing 4,4′-azobis(pyridine)

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Synthesis, structure and magnetic studies of two-dimensional network of Cu(II) polymer using malonate and 4,4′-azobispyridine ligands

Cited by 16 publications

References 57 publications

Pillaring Role of 4,4′-Azobis(pyridine) in Substituted Malonate-Containing Manganese(II) Complexes: Syntheses, Crystal Structures, and Magnetic Properties

Pillaring Role of 4,4′-Azobis(pyridine) in Substituted Malonate-Containing Manganese(II) Complexes: Syntheses, Crystal Structures, and Magnetic Properties

Reactions of Low-Valent Titanocene(II) Fragments with trans-4,4′-Azobispyridine (RN═NR, R = C5H4N): Formation of Tetranuclear Molecular Squares by trans−cis Isomerization

Synthesis, spectroscopic and electrochemical characterization and molecular structure of polypyridyl ruthenium complexes containing 4,4′-azobis(pyridine)

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Reactions of Low-Valent Titanocene(II) Fragments with trans-4,4′-Azobispyridine (RN═NR, R = C₅H₄N): Formation of Tetranuclear Molecular Squares by trans−cis Isomerization