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

Abstract

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.

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

“…The ability of alkaline metal ions to bind Co II malonates was shown previously , , . Similar CPs of Ni II , Cu II , and Mn II were reported; notably, 3d metal malonates (Cu II ) can be bound by other 3d metal ions (Mn II ) …”

“…Dimethylmalonate was chosen as the ligand because the dianionic fragments {MMal 2 } (M = transition metal ion, Mal = malonate or substituted malonate) can be easily assembled in structures with high dimensionality, as well as in porous CPs, by linking with alkaline, alkaline‐earth, or transition metal ions . One more advantage of malonates is their high thermal stability, which is essential for studies of thermal dehydration processes , …”

Design and synthesis of coordination polymers with chelated units and their application in nanomaterials science

“…The O), where H 2 L is 1,1-cyclopropanedicarboxylic, 1,1-cyclobutanedicarboxylic and butylmalonic acid, respectively, occurs above 170 C and leads to the formation of BaCuO 2 . 356 It is important that the thermolysis conditions have effect on the phase compositions of nanomaterials and the formation of BaCuO 2 proceeds under milder conditions from latter CP than those from the rst two CPs.…”

Coordination Polymers Based on Oxovanadium(IV) Butylmalonate Fragments and Potassium, Magnesium, and Cadmium Cations

“…Substituted malonic acids (H 2 R 2 mal) play a special role among the representatives of this large class of ligands, since their anions are capable of forming six-membered chelate cycles with 3d-metal cations and, correspondingly, can form stable mononuclear bis-chelate anionic complexes [M(R 2 mal) 2 ] 2-(M = VO 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ ) containing free for coordination oxygen atoms of carboxyl groups. These complexes are promising as metal-containing blocks for assembling polynuclear structures and coordination polymers containing metal atoms of various types [27,28]. The nature of substituents (R) in a malonate anion affects not only the solubility of the reaction product in a specific reaction medium but its crystal structure.…”