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Two new dicarboxylate-based three-dimensional cobalt coordination polymers, [Co(Me 2 mal)(bpe) 0.5 (H 2 O)] n ( 1 ) and [Co(Me 2 mal)(bpe) 0.5 ] n ( 2 ), were synthesized from dimethylmalonic acid (H 2 -Me 2 mal) in temperature-controlled solvothermal reactions. Lower temperatures (6080 °C) favored the formation of 1 , while higher temperatures (120 °C) favored the production of 2. Compound 1 is comprised of Co(II) corrugated layers linked by syn - anti carboxylate bridges from the Me 2 mal 2- ligands and pillared through bis -monodentate bpe groups. Compound 2 is comprised of a three-dimensional network involving one-dimensional Co-carboxylate chains bonded by antisymmetric µ 4 -Me 2 mal 2- ligands and aligned parallel to the [001] direction. The solvothermal retreatment of crystalline samples of 1 in a DMF/H 2 O solvent at 120 °C allowed the structural reassembly, with complete conversion within 2 over 48 h. Magnetic analyses revealed that compound 1 exhibits both spin-orbital coupling and antiferromagnetic interactions through a syn - anti carboxylate (Me 2 mal 2- ) bridge exchange pathway [Co-Co separation of 5.478 Å] and compound 2 showed a ferromagnetic interaction resulting from the short Co-Co separation (3.150 Å) and the small Co-O-Co bridging angles (98.5° and 95.3°) exchange pathway which was provided by µ 4 -Me 2 mal 2- bridging ligand.

polymers

Temperature-Controlled Assembly/Reassembly of Two Dicarboxylate-Based Three-Dimensional Co(II) Coordination Polymers with an Antiferromagnetic Metallic Layer and a Ferromagnetic Metallic Chain