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′-biphenyl

Authors

James R. Gardinier, Marquette UniversityFollow
Heidi M. Tatlock, Marquette University
Jeewantha S. Hewage, Marquette UniversityFollow
Sergey V. Lindeman, Marquette UniversityFollow

Document Type

Article

Language

eng

Publication Date

7-23-2013

Publisher

American Chemical Society

Source Publication

Crystal Growth & Design

Source ISSN

1528-7483

Original Item ID

10.1021/cg400466k

Abstract

In the search for new examples of systems that self-assemble into cyclic metal–organic architectures, the six isomers of X,Y′-bis(di(1H-pyrazolyl)methane)-1,1′-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′-bis(di(1H-pyrazolyl)methane)-1,1′-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° 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.

Comments

Crystal Growth & Design, Vol. 13, No. 9 (July 23, 2013): 3864-3877. DOI. © 2013 American Chemical Society. Used with permission.

Recommended Citation

Gardinier, James R.; Tatlock, Heidi M.; Hewage, Jeewantha S.; and Lindeman, Sergey V., "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′-biphenyl" (2013). Chemistry Faculty Research and Publications. 564.
https://epublications.marquette.edu/chem_fac/564