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Metal Complexes Based on Tetrathiafulvalene-Fused π-Extended Schiff Base Ligands – Syntheses, Characterization, and Properties

Authors

  • Jie Qin,

    1. State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China, Fax: +86-25-83314502
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  • Chen-Xi Qian,

    1. State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China, Fax: +86-25-83314502
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  • Nan Zhou,

    1. State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China, Fax: +86-25-83314502
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  • Rong-Mei Zhu,

    1. State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China, Fax: +86-25-83314502
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  • Yi-Zhi Li,

    1. State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China, Fax: +86-25-83314502
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  • Jing-Lin Zuo,

    1. State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China, Fax: +86-25-83314502
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  • Xiao-Zeng You

    1. State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China, Fax: +86-25-83314502
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Abstract

π-Conjugated tetrathiafulvalene (TTF)-based donors with a monoamine moiety, 2-[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-1,3-benzodithiol-5-amine (La) and 2-(5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-1,3-benzodithiol-5-amine (Lb), have been synthesized. Condensation of the TTF amines with different pyridinecarbaldehydes afforded new TTF-fused π-extended Schiff base ligands, La-imine-4-pyridyl (L1), La-imine-3-pyridyl (L2), and Lb-imine-2-pyridyl (L3). Four metal complexes based on these Schiff base pyridine ligands, M(hfac)2(L)2 (M = CuII, L = L1, 4; M = MnII, L = L1, 5; M = CuII, L = L2, 6; hfac = hexafluoroacetylacetonate) and [Re(CO)4(L3)][Re2(CO)6Cl3] (7), have been synthesized and structurally characterized. The ligands in all of the complexes show a near planar structure, and the different coordination modes of the metal ions and relative orientation of the terminal N donors result in a different crystalline organization in the solid state. The absorption spectra and redox behavior of these new compounds have been studied. These paramagnetic complexes are promising building blocks for the construction of multifunctional materials due to their planar structures and inherent redox properties.

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