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Synthesis and Structural Diversity of d10 Metal Coordination Polymers Constructed from New Semirigid Bis(3-methyl-1H-pyrazole-4-carboxylic acid)alkane Ligands

Abstract

Three isomeric bis(3-methyl-1H-pyrazole-4-carboxylic acid)alkane Ligands (H2L1, H2L2 and H2L3) were prepared via a two-step process from ethyl 3-methyl-1H-pyrazole-4-carboxylate (1). They were introduced as bridging ligands to assemble with Zn(II) and Cd(II) ions, two chiral coordination polymers [Zn(L1)(DMF)(H2O)]n (3a and 3b), [Cd(L1)(H2O)]n·nH2O (5) and two achiral coordination polymers [Zn(L1)(H2O)2]n·nH2O (4), [Cd(L2)(H2O)]n·2nH2O·nEtOH (6) were obtained. The (L1)2‒ adopts trans-conformation in 3, leading to the formation of 1D coordination chain, and the 2D coordination layers in 4‒6 are constructed by (L1)2–/(L2)2– anions in cis-conformation. Notably, the structures of 3a and 3b exhibit H-bonded chiral 2D network, featuring a right-handed 3-fold helix in 3a, while a left-handed 3-fold helix in 3b. Compound 5 possesses a 3D supramolecular network with homochiral left-handed helical chains. Whose chirality is due solely to the hydrogen-bonds. The chiral nature of enantioenriched 3a produced by diffusion crystallization was confirmed by solid-state CD spectroscopy. The thermal and luminescence properties of 3–6 in the solid state have also been investigated.

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Publication details

The article was received on 13 Mar 2017, accepted on 10 May 2017 and first published on 10 May 2017


Article type: Paper
DOI: 10.1039/C7NJ00835J
Citation: New J. Chem., 2017, Accepted Manuscript
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    Synthesis and Structural Diversity of d10 Metal Coordination Polymers Constructed from New Semirigid Bis(3-methyl-1H-pyrazole-4-carboxylic acid)alkane Ligands

    M. Cheng, Q. Wang, J. Bao, Y. Wu, L. Sun, B. Yang and Q. Liu, New J. Chem., 2017, Accepted Manuscript , DOI: 10.1039/C7NJ00835J

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