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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Four new Zn(ii) and Cd(ii) coordination polymers using two amide-like aromatic multi-carboxylate ligands: synthesis,
Qiuxia Cheng1, Luzhu Qin1, Chunxian Ke1
1School of Chemistry and Environment, South China Normal University, Guangzhou Key Laboratory of Materials for Energy Conversion and Storage 510006 P. R. China linxm@scnu.edu.cn caiyp@scnu.edu.cn.
Abstract:
Four new coordination polymers, {[Zn(3-PBI)(H2O)]·2DMF} (1), [Cd(3-PBI)(DMF)] (2), {[Zn4(μ4-O)(4-PBI)3]·3DMF} (3), {[Cd4(4-PBI)4(H2O)6]·13H2O} (4), have been constructed from two isomeric flexible multi-carboxylate ligands, 3-H2PBI = 5-(3-(pyridin-3-yl)benzamido)isophthalic acid and 4-H2PBI = 5-(3-(pyridin-4-yl)benzamido)isophthalic acid. Structural analysis reveals that compound 1 is a one-dimensional (1D) ladder-like chain assembled by Zn(ii) ions and 3-PBI2- ligands, which further extend into a 3D supramolecular structure through π⋯π stacking and interlayer (O-H⋯O) hydrogen bonding interactions. In compound 2, Cd2+ metal ions are connected by carboxylate groups to form [Cd2(COO)4] secondary building units (SBUs). The whole framework possesses a quadrilateral channel and constitutes a unique 3D (3,6)-connected rutile net with the Schläfli symbol of (42·610·83)(4·62)2. As for 3, Zn(ii) ions are bridged by one μ4-O and six carboxylate groups to form a tetranuclear [Zn4(μ4-O)(COO)6] cluster, resulting in a rare (3,9)-connected 3D network. Compound 4 has an appealing 2D layered architecture involving two distinct topologies in the crystal structure, stacking in an unusual ABBABB mode (where A represents (4·82) topology and B denotes kgd topology). Moreover, compound 2 is prepared as a support for active selenium through a melt-diffusion method. The obtained Cd-CP/Se electrode can be tested for lithium-selenium batteries and shows an initial capacity of 514 mA h g-1 and a reversible capacity of 200 mA h g-1 at 1C after 500 cycles. The good storage performance of Cd-CP/Se demonstrates it to be a prospective cathode material for lithium-selenium batteries.
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