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Three transition metal complexes with uncoordinated carboxyl groups: synthesis, structures, and luminescence properties

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Abstract

A new ligand 1-carboxymethyl-5-methyl-1H-pyrazole-4-carboxylic acid (H2L1) and its isomer 1-carboxymethyl-3-methyl-1H-pyrazole-4-carboxylic acid (H2L2) have been synthesized and characterized by IR and 1H NMR. Three complexes of these ligands, [M(HL1)2(H2O)2] (1: M = Zn; 2: M = Cu) and [Cd(HL2)2(H2O)2] (3) were synthesized by the reactions of H2L1 or H2L2 with the corresponding M(NO3)2·6H2O. The complexes were characterized by physico-chemical and spectroscopic methods, single-crystal X-ray diffraction, and thermogravimetric analysis. Complexes 1 and 2 are isostructural, while complex 3 crystallizes in the triclinic system. The M(II) atom in each of the complexes has a distorted octahedral geometry involving two oxygen and two nitrogen atoms from two anionic (HL1)− or (HL2)− ligands and two oxygen atoms from water ligands. Adjacent monomeric components are connected by hydrogen bonds to form a 3D supramolecular network. The free ligands and complexes 1 and 3 show dual-emissive luminescence in the solid state at room temperature. The luminescence intensity of solid complex 1 is weakened in the presence of NH3.

Graphical Abstract

Two new isomers, H2L1 and H2L2, and three complexes, [Zn(HL1)2(H2O)2], [Cu(HL1)2(H2O)2], and [Cd(HL2)2(H2O)2] have been synthesized, which display dual-emissive luminescence in the solid state.

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Acknowledgments

The authors are particularly grateful to the Natural Science Foundation of China (Nos. 20971060 and 21101018), the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions, and the Natural Science Foundation of State Key Laboratory of Coordination Chemistry for the financial support.

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Authors and Affiliations

  1. School of Petrochemical Engineering and Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Changzhou University, Changzhou, 213164, Jiangsu, People’s Republic of China

    Sen Su, Mei-ling Cheng, Yanqiu Ren, Changwei Zhai, Feng Tao & Qi Liu

  2. State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210093, Jiangsu, People’s Republic of China

    Qi Liu

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  1. Sen Su
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  2. Mei-ling Cheng
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  3. Yanqiu Ren
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  4. Changwei Zhai
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  5. Feng Tao
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  6. Qi Liu
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Corresponding author

Correspondence to Qi Liu.

Electronic supplementary material

Below is the link to the electronic supplementary material.

11243_2014_9833_MOESM1_ESM.doc

CCDC 958411, 962642, and 973934 contain the supplementary crystallographic data for the three complexes 1, 2, and 3. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: (internet) þ 44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk. (DOC 3276 kb)

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Su, S., Cheng, Ml., Ren, Y. et al. Three transition metal complexes with uncoordinated carboxyl groups: synthesis, structures, and luminescence properties. Transition Met Chem 39, 559–566 (2014). https://doi.org/10.1007/s11243-014-9833-x

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  • DOI: https://doi.org/10.1007/s11243-014-9833-x

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