Issue 45, 2013

Alkali-metal-regulated construction of superhydrophilic ZnII and CdII coordination polymers with perhalogenated terephthalate ligands

Abstract

By simply introducing different alkali metal ions as structure-directing agents, four new coordination polymers with the formulae [Cd3(BDC-F4)3(DMF)2(MeOH)6]n (1), [Cd(BDC-F4)(DMF)2(H2O)2]n (2), [Zn2Na2(BDC-Cl4)3(DMF)42-MeOH)]n (3) and [ZnK(BDC-Cl4)1.5(DMF)(Me2NH)]n (4) (BDC-F4 = 2,3,5,6-tetrafluoro-benzenedicarboxylate; BDC-Cl4 = 2,3,5,6-tetrachloro-benzenedicarboxylate; DMF = dimethylformamide and Me2NH = dimethylamine) have been synthesized and structurally characterized. Complex 1 presents an open three-dimensional (3D) 3-nodal (3,4)-connected framework, 2 has a one-dimensional (1D) chain structure, 3 features a 3D 4-nodal (3,4,5,6)-connected coordination network constructed from the new ZnII–NaI heterometallic tetranuclear cluster, and 4 shows a 3D 4-nodal (3,5,6)-connected network based on the unique ZnII–KI heterometallic tetranuclear cluster. The results reveal the significant influence of alkali-metal ions on the structural topologies of complexes 1–4. Interestingly, compounds 1–4 all exhibit high water solubility, and futher evaporation of their water solution will result in a 1D coordination polymer {[Cd4(BDC-F4)4(H2O)11]·3.5H2O}n (5) consisting of the unprecedented polymeric [CdII–H2O]n chain, and a zero-dimensional (0D) complex [Zn(H2O)6]·(BDC-Cl4)·4H2O (6) containing the discrete [Zn(H2O)6]2+ cationic and BDC-Cl4 dianionic moieties. Furthermore, the solution chemistry of complexes 5 and 6 has been investigated by electrospray ionization (ESI) mass spectrometry and molar electrical conductivity. The photoluminescent properties of complexes 1–6 have also been explored, which interestingly indicate a strong blue emission of complex 1 in the solid state at room temperature.

Graphical abstract: Alkali-metal-regulated construction of superhydrophilic ZnII and CdII coordination polymers with perhalogenated terephthalate ligands

Supplementary files

Article information

Article type
Paper
Submitted
11 jun 2013
Accepted
08 aug 2013
First published
09 aug 2013

CrystEngComm, 2013,15, 9613-9622

Alkali-metal-regulated construction of superhydrophilic ZnII and CdII coordination polymers with perhalogenated terephthalate ligands

S. Chen, Z. Zhang, K. Huang, H. Luo, M. He, M. Du and Q. Chen, CrystEngComm, 2013, 15, 9613 DOI: 10.1039/C3CE41108G

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