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Issue 6, 2015
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Synthesis, structural versatility and magnetic properties of a series of copper(II) coordination polymers based on bipyrazole and various dicarboxylate ligands

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Abstract

Seven new copper(II) coordination networks combining flexible 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (bpz) and diverse dicarboxylates, [Cu(bpz)0.5(adip)]n (1), [Cu2(bpz)4(sub)2]n (2), [Cu4(bpz)1.5(aze)·H2O]n (3), [Cu2(bpz)(pta)2(H2O)·H2O]n (4), [Cu2(bpz)(ipa)]n (5), [Cu2(bpz)(o-pda)2·H2O]n (6), and [Cu23-OH)(bpz)(p-pda)1.5·H2O]n (7) (H2adip = adipic acid, H2sub = suberic acid, H2aze = azelaic acid, H2pta = phthalic acid, H2ipa = isophthalic acid, H2o-pda = o-phenylenediacetic acid, H2p-pda = p-phenylenediacetic acid), have been obtained under solvothermal conditions and structurally verified by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, powder X-ray diffraction (PXRD), infrared spectroscopy (IR), UV-vis spectroscopy and thermogravimetric analyses (TGA). Single crystal X-ray diffraction analysis revealed that both 1 and 6 are 6-connected pcu networks (point symbol: {412·63}) based on paddle-wheel [Cu2(COO)4] secondary building units (SBU). Complexes 2 and 4 are 2D 44-sql networks based on a single metal ion node and a binuclear [Cu2(COO)4(H2O)] SBU, respectively, while complex 3 features an extremely rare 3D 5-connected hxg-d-5-C2/c (point symbol: {42·67·8}) network. Complex 5 shows a 1D tape structure built from bpz sealed 1D helical Cu2(ipa) chains along the b axis, and 7 is a 3D 8-connected hex (point symbol: {36·418·53·6}) network based on a centrosymmetric [Cu43-OH)2(COO)4] SBU. A thorough structural comparison of these coordination networks suggests that the coordination fashions, conformations of dicarboxylates along with the different inorganic Cu(II) SBUs simultaneously play a significant role in constructing the diverse networks. Variable-temperature magnetic susceptibility data denote that 4 and 7 display antiferromagnetic interactions in binuclear [Cu2(COO)4(H2O)] and [Cu43-OH)2(COO)4] SBUs. Moreover, the thermal stability and UV-vis spectra of 1–7 are discussed in detail.

Graphical abstract: Synthesis, structural versatility and magnetic properties of a series of copper(ii) coordination polymers based on bipyrazole and various dicarboxylate ligands

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Publication details

The article was received on 13 Nov 2014, accepted on 15 Dec 2014 and first published on 15 Dec 2014


Article type: Paper
DOI: 10.1039/C4CE02248C
Citation: CrystEngComm, 2015,17, 1405-1415
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    Synthesis, structural versatility and magnetic properties of a series of copper(II) coordination polymers based on bipyrazole and various dicarboxylate ligands

    L. Han, S. Wang, Z. Jagličić, S. Zeng, J. Zheng, Z. Li, J. Chen and D. Sun, CrystEngComm, 2015, 17, 1405
    DOI: 10.1039/C4CE02248C

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