Step-by-step thermal transformations of a new porous coordination polymer [(H2O)5CuBa(Me2mal)2]  (Me2mal2−=dimethylmalonate): Thermal degradation to barium cuprate

Zauzolkova, N. V.; Dobrokhotova, Zhanna V.; Lermontov, A. S.; Zorina, E. N.; Емелина, А. Л.; Bukov, Mikhail A.; Чернышев, Владимир В.; Сидоров, А. А.; Кискин, М. А.; Bogomyakov, A. S.; Lytvynenko, Anton; Kolotilov, Sergey V.; Velikodnyi, Yu. A.; Kovba, M. L.; Новоторцев, В. М.; Еременко, И. Л.

doi:10.1016/j.jssc.2012.09.014

Cited by 34 publications

(18 citation statements)

References 71 publications

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“…In all of the isolated complexes 1-4, similarly to the majority of reported analogues, [18,19,22,23] the structural unit is the bischelate dianion moiety {Cu(R 2 mal) 2 } 2-. It consists of a copper(II) atom coordinated to four oxygen atoms of carboxyl groups in two chelate-bound dianions of substituted malonic acid R 2 mal 2-.…”

Section: Synthesis and Structural Studies Of 1-4supporting

confidence: 54%

“…[18] In this work aimed at the optimization of the processes for the synthesis of heterometallic {Ba-Cu} malonates and the study of the effect of various organic substituents in the carboxylate anion on the architecture and nature of the final polynuclear structures, we studied the reactions in the "H 2 R 2 mal-Ba(OH) 2 (4).…”

Section: Synthesis and Structural Studies Of 1-4mentioning

confidence: 99%

“…[18] The structural similarity of the dimethylmalonate and 1,1-cyclobutanedicarboxylate compounds is probably due to the similarity of the volumes of the substituents of the malonic acid.…”

Section: Synthesis and Structural Studies Of 1-4mentioning

confidence: 99%

“…[14][15][16] The heterometallic β-diketonate [LiMn 2 (thd) 5 ] (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate) is a molecular precursor (decomposition in air/oxygen at 600°C) for nanosized particles of the spinel-type oxide LiMn 2 O 4 , a cathode material for lithium-ion batteries. [17] Previously, we have shown that a stoichiometric BaCuO 2 phase can be formed by the stepwise thermolysis of threedimensional porous [BaCu(Me 2 mal) 2 (H 2 O) 5 ] n polymer (5, H 2 Me 2 mal is dimethylmalonic acid), [18] in which the complex bischelate dianionic moiety {Cu(Me 2 mal) 2 } 2-is the main structure-forming unit. A further study of the reaction products of {Cu(Me 2 mal) 2 } 2-with different cations (alkaline metals, alkaline-earth metals) demonstrated that the self-assembly of various types of structures is possible.…”

Section: Introductionmentioning

confidence: 99%

“…A further study of the reaction products of {Cu(Me 2 mal) 2 } 2-with different cations (alkaline metals, alkaline-earth metals) demonstrated that the self-assembly of various types of structures is possible. [18,19] Furthermore, a cage structure containing cyclic structural motifs only formed for dimethylmalonate polymers with barium ions and was preserved as the transition metal atoms in {M(Me 2 mal) 2 } 2-were changed (M = Co, Zn). [20] However, the use of a fragment with unsubstituted malonate anions {Cu(mal) 2 } 2-(H 2 mal = malonic acid) as a building block under similar conditions did not allow the assembly of high-dimensional structures.…”

Section: Introductionmentioning

confidence: 99%

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The Use of Malonate Coordination Polymers with Cu^II and Ba^II Atoms for Barium Cuprate Preparation

et al. 2015

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The reactions of CuSO4·5H2O and Ba(R2mal) [R2mal2– is the dianion of 1,1‐cyclopropanedicarboxylic acid (H2Cpdc), 1,1‐cyclobutanedicarboxylic acid (H2Cbdc), or butylmalonic (H2Bumal) acid] in water give crystals of the 3D coordination polymers [BaCu(Cpdc)2]n (1), [BaCu(Cbdc)2(H2O)]n (2) and [Ba3Cu3(Bumal)6(H2O)11]n·2n(H2O) (3). The heating of 2 in air to 200 °C for 60 min results in the removal of the coordinated water molecules to give anhydrous [BaCu(Cbdc)2]n (4). The structures of 1–3 were determined by single‐crystal XRD, and that of 4 was derived from powder XRD (XPRD) data. It was assumed that the crystal structures of the polymer complexes that we isolated were determined, to a considerable extent, by the nature of the substituent of the dicarboxylic acid. For 2, the dicarboxylic acid contains closed cyclic moieties, which are retained during dehydration to give 4. A comparative study of the thermal decomposition processes and thermal kinetics of 1–3 showed that the dehydration proceeds by a single scheme, and the bonds between the structural moieties in the anhydrous intermediates become stronger. The thermal destruction of the anhydrous compounds 1, 4 and {3} [the dehydrated intermediate of the thermal decomposition of 3, as proved by thermogravimetric analysis (TGA) data] occurs above 170 °C. The phase compositions of their solid products are determined by the thermolysis conditions, and the formation of BaCuO2 from 3 can be realized under milder conditions than those for the formation from 1 and 2.

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Section: Synthesis and Structural Studies Of 1-4supporting

confidence: 54%

Section: Synthesis and Structural Studies Of 1-4mentioning

confidence: 99%

“…[18] The structural similarity of the dimethylmalonate and 1,1-cyclobutanedicarboxylate compounds is probably due to the similarity of the volumes of the substituents of the malonic acid.…”

Section: Synthesis and Structural Studies Of 1-4mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Use of Malonate Coordination Polymers with Cu^II and Ba^II Atoms for Barium Cuprate Preparation

et al. 2015

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Chemical Design of Heterometallic Coordination Polymers Based on {Cu(Me₂mal)₂} Fragment

et al. 2016

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Topological methods of analysis of coordination networks have become an integral part of design of coordination polymers, MOFs, and zeolites. It helps to chemists to understand the novelty of findings, to reveal relations between different structures, to propose new design concepts, and to communicate effectively with each other. However, this is not the limit of the methods. Description of coordination environment of structural units (metal atoms, ligands, SBUs), network topology (topological type), and topology of entanglement (entanglement pattern) intrinsically leads to finding relations between the topological parameters. Further, the correlations can be grouped (systematized) in a hierarchical manner to produce a knowledge database for design and prediction of new materials (their structure and properties) [1, 2]. Thus, new structural characteristics, the so-called descriptors, have to be invented for prediction of particular structural features. For example, we have proposed to use topological type of Hopf ring net for analysis of topology entanglements in coordination networks. Now we put forward Extended ring net (ERN), which incorporates information about topology of entangled nets and topology of entanglements. ERN is able to distinguish patterns of entanglements up to isomorphism and polymorphism, that allowed us to describe new type of isomerism of coordination polymers, entanglement isomerism. MOF structures are usually considered as a result of assembly of secondary building units in an isoreticular manner. Usually SBU is considered as a topologically dense 0D polynuclear complex group, which coordination figure is predetermined by orientation of points of extension (functional groups of ligands connected by linkers). However, many practically important MOFs contain infinite SBUs; e.g. rod-shaped 1D {AlOH(CO2)2} groups are connected by benzene linkers in parallel fashion into framework MIL-53. We have produced a comprehensive systematics of infinite SBUs and ways for their connection with new algorithms of rod-MOFs description as 2D net of rods connections. Selection of correct structural groups is also important for design of self-catenated networks. We proposed a universal algorithm for selection of all reasonable subnets and determining the structure driving ones. To describe the geometry and topology of voids and channels in porous structures we combined topological methods and Voronoi partitioning. The improved Voronoi partitioning provides much more characteristics of porous structures, e.g. periodicity, topology and crystallographic orientation of channels, minimal cages of framework, open sights of metal atoms etc. These descriptors give us an opportunity to define metal-organic nanotube as a 1-periodic tiling of face-shared 3D tiles. To enhance the usability of the results of topological analysis we collected values of descriptors into a knowledge database [2]. The database was applied in finding relations between topological parameters for heterometallic coordination polymers based on {C...

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2D Coordination Polymer Built from Lithium Dimethylmalonate and Co^II Ions: The Influence of Dehydration on Spectral and Magnetic Properties

et al. 2017

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2D coordination polymer [Li 2 Co(H 2 O) 4 (Me 2 Mal) 2 ] n (1) was synthesized by interaction of lithium dimethylmalonate (Li 2 Me 2 mal) and cobalt(II) acetate. The structure of 1 can be described as {Li(H 2 O) 2 (Me 2 Mal-κ-O,O′)} anions linked by Co II cations through bridging water molecules and Me 2 Mal 2dianions. Upon heating to 130-190°C, compound 1 loses water molecules and transforms into [Li 2 Co(Me 2 Mal) 2 ] n (2). Compound 2 is non-porous and amorphous, its rehydration by water leads to formation of 1, as shown by powder XRD. Dehydration of 1 is associated with a drastic color change from pink to violet. The temperature dependency of magnetic susceptibility M for Coordination polymers (CP) have unique potential to prepare compounds with desired optical, magnetic, sorption or catalytic properties, because the metal ions, polynuclear building blocks, and bridging ligands can be varied over a wide range. [1][2][3] Combination of several properties in one compound, especially the ability to change certain characteristic under the action associated with another property, can be utilized for creation of materials with tunable properties, which can be used as active bodies for optical, magnetic or conducting sensors, displays, indicators, etc. [4,5] For example, the reversible uptake of guest molecules can lead to a change of optical (color), [6][7][8] magnetic properties (magnetic susceptibility, temperature of spin-crossover, or magnetic ordering), [8][9][10][11] or luminescence. [12][13][14] Such changes are often associated with structural transformations, [a] N.1396 Figure 2. Topological representations of the underlying network (a) and further simplified binodal 3,6-connected net 3 2 6 1 topology kgd (b) for 1. Key: Li I : yellow, Co II : pink, Me 2 Mal 2-: blue.

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Step-by-step thermal transformations of a new porous coordination polymer [(H2O)5CuBa(Me2mal)2] (Me2mal2−=dimethylmalonate): Thermal degradation to barium cuprate

Cited by 34 publications

References 71 publications

The Use of Malonate Coordination Polymers with Cu^II and Ba^II Atoms for Barium Cuprate Preparation

The Use of Malonate Coordination Polymers with Cu^II and Ba^II Atoms for Barium Cuprate Preparation

Chemical Design of Heterometallic Coordination Polymers Based on {Cu(Me₂mal)₂} Fragment

2D Coordination Polymer Built from Lithium Dimethylmalonate and Co^II Ions: The Influence of Dehydration on Spectral and Magnetic Properties

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Step-by-step thermal transformations of a new porous coordination polymer [(H2O)5CuBa(Me2mal)2] (Me2mal2−=dimethylmalonate): Thermal degradation to barium cuprate

Cited by 34 publications

References 71 publications

The Use of Malonate Coordination Polymers with CuII and BaII Atoms for Barium Cuprate Preparation

The Use of Malonate Coordination Polymers with CuII and BaII Atoms for Barium Cuprate Preparation

Chemical Design of Heterometallic Coordination Polymers Based on {Cu(Me2mal)2} Fragment

2D Coordination Polymer Built from Lithium Dimethylmalonate and CoII Ions: The Influence of Dehydration on Spectral and Magnetic Properties

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Product

Resources

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The Use of Malonate Coordination Polymers with Cu^II and Ba^II Atoms for Barium Cuprate Preparation

The Use of Malonate Coordination Polymers with Cu^II and Ba^II Atoms for Barium Cuprate Preparation

Chemical Design of Heterometallic Coordination Polymers Based on {Cu(Me₂mal)₂} Fragment

2D Coordination Polymer Built from Lithium Dimethylmalonate and Co^II Ions: The Influence of Dehydration on Spectral and Magnetic Properties