Self‐Assembly of 3,6‐Bis(4‐triazolyl)pyridazine Ligands with Copper(I) and Silver(I) Ions: Time‐Dependant 2D‐NOESY and Ultracentrifuge Measurements |
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Authors: | Bobby Happ Dr Georges M Pavlov Esra Altuntas Christian Friebe Dr Martin D Hager Dr Andreas Winter Dr Helmar Görls Dr Wolfgang Günther Prof?Dr Ulrich S Schubert |
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Institution: | 1. Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich‐Schiller‐University Jena, Humboldtstr.?10, 07743 Jena (Germany), Fax: (+49)?3641‐9482‐02;2. Laboratory of Inorganic and Analytical Chemistry, Friedrich‐Schiller‐University Jena, Lessingstra?e?8, 07743 Jena (Germany) |
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Abstract: | Two 3,6‐bis(R‐1H‐1,2,3‐triazol‐4‐yl)pyridazines (R=mesityl, monodisperse (CH2? CH2O)12CH3) were synthesized by the copper(I)‐catalyzed azide–alkyne cycloaddition and self‐assembled with tetrakis(acetonitrile)copper(I) hexafluorophosphate and silver(I) hexafluoroantimonate in dichloromethane. The obtained copper(I) complexes were characterized in detail by time‐dependent 1D 1H, 13C] and 2D 1H‐NOESY] NMR spectroscopy, elemental analysis, high‐resolution ESI‐TOF mass spectrometry, and analytical ultracentrifugation. The latter characterization methods, as well as the comparison to analog 3,6‐di(2‐pyridyl)pyridazine (dppn) systems and their corresponding copper(I) and silver(I) complexes indicated that the herein described 3,6‐bis(1H‐1,2,3‐triazol‐4‐yl)pyridazine ligands form 2×2] supramolecular grids. However, in the case of the 3,6‐bis(1‐mesityl‐1H‐1,2,3‐triazol‐4‐yl)pyridazine ligand, the resultant red‐colored copper(I) complex turned out to be metastable in an acetone solution. This behavior in solution was studied by NMR spectroscopy, and it led to the conclusion that the copper(I) complex transforms irreversibly into at least one different metal complex species. |
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Keywords: | analytical ultracentrifugation heterocycles NMR spectroscopy self‐assembly supramolecular chemistry |
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