Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism

Abstract

Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior.

Morphological variations in Bi2S3 nanoparticles synthesized by using a single source precursor

“…The variation in morphology of nanoparticles during the solvothermal process, could be attributed to their growth mechanisms. This is dependent on the capping agent, which acts by suppressing the growth of certain crystal facet via coordination to the metal cations [ 50 ]. The properties of the capping agents have been reported to play important role in controlling both the size and morphology of nanoparticles [ 51 ].…”

Ce-Doped Graphitic Carbon Nitride Derived from Metal Organic Frameworks as a Visible Light-Responsive Photocatalyst for H2 Production

“…DMF has medium binding ability with metal cations, resulting in the formation of a new crystalline phase. However, this binding ability is not strong enough to intercalate within the coordination frameworks [46]. Therefore, in this work we use a mixed solvent system to obtain optimal structures.…”

Reductive and Coordinative Effects of Hydrazine in Structural Transformations of Copper Hydroxide Nanoparticles

“…Further elucidation of shape transformations of copper oxide nanoparticles upon oxidation or reduction would expand the toolbox of preparative nanochemistry and enable the development of superior functional materials for energy and catalysis. Morphological transformations of amorphous copper oxide nanomaterials are of particular interest; the absence of short-range order could allow for integration or entrapment of polydentate ligands within the material upon changes in the oxidation state [28], introducing compositional moieties similar to metal-organic coordination polymers [29,30], which represents an unexplored and promising avenue of composite materials from both synthetic and application standpoints.…”