Cyclic versus Polymeric Supramolecular Architectures in Metal Complexes of Dinucleating Ligands: Silver(I) Trifluoromethanesulfonate Complexes of the Isomers of Bis(di(1H-pyrazolyl)methyl)-1,1鈥?biphen

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• 作者：James R. Gardinier ; Heidi M. Tatlock ; Jeewantha S. Hewage ; Sergey V. Lindeman
• 刊名：Crystal Growth & Design
• 出版年：2013
• 出版时间：September 4, 2013
• 年：2013
• 卷：13
• 期：9
• 页码：3864-3877
• 全文大小：875K
• 年卷期：v.13,no.9(September 4, 2013)
• ISSN：1528-7505

文摘

In the search for new examples of systems that self-assemble into cyclic metal鈥搊rganic architectures, the six isomers of X,Y鈥?bis(di(1H-pyrazolyl)methane)-1,1鈥?biphenyl, L_XY, and their silver(I) trifluoromethanesulfonate complexes were prepared. Five of the six silver complexes gave crystals suitable for single crystal X-ray diffraction, with only the microcrystalline derivative of 2,3鈥?bis(di(1H-pyrazolyl)methane)-1,1鈥?biphenyl, L₂₃, proving to be unsuitable for this analysis. Of the structurally characterized silver(I) complexes, that with L₂₂ showed an unusual trans-spanning chelating coordination mode to silver. At the same time the ligand was also bound to a second silver center giving rise to a cyclic supramolecular isomer with a 22-membered metallacycle. The complex of L₃₄ also gave a cyclic dication but with a remarkable 28-membered metallacycle ring. The remaining three derivatives were polymeric. The results of this study underscore that a 120掳 angle between dipyrazolylmethyl moieties across aromatic spacers will give rise to a cyclic dication but this is not an exclusive requirement for the formation of cyclic architectures. Also, the supramolecular structures of complexes are assembled via a variety of noncovalent interactions involving the di(pyrazolyl)methyl cation most notably by weak hydrogen bonding interactions involving the methine hydrogen and an oxygen atom of the triflate anion.