Abstract
The synthesis of 1D cobalt and zinc monometallic and heterometallic coordination polymers (CPs) was carried out applying one-pot synthetic methods by using either supercritical carbon dioxide or ethanol as the solvent. A collection of four 1D CPs were thus obtained by the combination of a metal (or a mixture of metals) with the linker 1,4-bis(4-pyridylmethyl)benzene. The used metallic complexes were zinc and cobalt hexafluoroacetylacetonate, which can easily incorporate pyridine ligands in the coordination sphere of the metal centre. Independently of the used solvent, the precipitated phases involving Zn(ii), i.e., homometallic CP of Zn(ii) and bimetallic CP of Zn(ii)/Co(ii), were isostructural. Contrarily, homometallic CPs of Co(ii) were precipitated as an isostructural phase of Zn(ii) or with a different structure, depending on the used solvent. All the structures were resolved by XRD using synchrotron radiation. In addition, the magnetic properties of the new CPs involving Co(ii) were studied. Remarkably, at low temperatures with the application of an external field, they acted as field-induced single molecule magnets.
Highlights
Coordination polymers (CPs) or metal–organic frameworks (MOFs) comprise metal nodes, usually transition metals or metallic clusters, connected in a crystalline network by multipodal organic linkers and coordination bonds
This design is used for compounds involving exible organic linkers, which are difficult to crystallize in networks with high symmetry factors
The interest of this study is to demonstrate the feasibility of using one-pot coprecipitation methods, performed in either green supercritical CO2 or ethanol (EtOH), to develope heterometallic systems
Summary
Coordination polymers (CPs) or metal–organic frameworks (MOFs) comprise metal nodes, usually transition metals or metallic clusters, connected in a crystalline network by multipodal organic linkers and coordination bonds. One of the unique features of these extended structures is the tunability in the design, based on the concept of the modi cation of the composition and geometry of the repeating unit This includes the use of different organic linkers or metal clusters, and the preparation of multivariate CPs with more than one linker and/or inorganic building unit in the design.. One of the earliest synthetic routes described to introduce heterogeneity in CPs was through the organic part, by pre-mixing in the solvothermal synthesis more than one bridging unit. This design is used for compounds involving exible organic linkers, which are difficult to crystallize in networks with high symmetry factors. Pioneering studies in bimetallic networks concern compounds with several inorganic
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