Influence of the cis/trans configuration on the supramolecular aggregation of aryltriazoles.

Sara Tejera,Javier González-Platas,Giada Caniglia,Andrea Favero,Rosa L Dorta,Jesús T Vázquez

doi:10.3762/bjoc.15.282

Sara Tejera, Javier González-Platas + Show 4 more

Open Access

https://doi.org/10.3762/bjoc.15.282

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Abstract

The ability of trans- and cis-1,2-glucopyranosyl and cyclohexyl ditriazoles, synthesized by CuAAC "click" chemistry, to form gels was studied, their physical properties determined, and the self-aggregation behavior investigated by SEM, X-ray, and EDC studies. The results revealed that self-assembly was driven mainly by π–π stacking interactions, in addition to hydrogen bonding, with the aromatic rings adopting a high degree of parallelism, as seen in crystal packings and ECD data. Furthermore, π–bromine interactions between the bromine atom of the aryl substituents and the triazole units might also contribute to an overall stabilization of the supramolecular aggregation of bis(4-bromophenyl)triazoles. The trans or cis spatial disposition of the triazole rings is highly important for gelation, with the cis configuration having higher propensity.

Highlights

Structures self-assembled by noncovalent interactions give rise to supramolecular architectures with specific physical and/or chemical properties
During the synthesis and characterization process of glucosyl mono- and ditriazole derivatives, which we carried out in order to analyze the use of aryltriazoles for the determination of absolute configuration [15], we serendipitously discovered that these glucosyl ditriazoles led to gels
The capacity of di-1,4-disubstituted 1,2,3-triazoles to form gels was studied taking the dependence on the trans/cis configuration of the molecules into account

Summary

Introduction

Structures self-assembled by noncovalent interactions give rise to supramolecular architectures with specific physical and/or chemical properties. Gels from low-molecular-weight gelators have potential applications in high-tech materials [1,2,3] and biomedical sciences [3,4,5,6]. Triazole derivatives have shown excellent gelation properties [7,8,9,10], in addition to a broad range of biological activities [11,12,13,14]. We carried out the corresponding supramolecular studies and report the ability of ditriazoles to form gels, their physical properties, as well as the dependence of these properties on the cis/trans relative configuration.

Results and Discussion

Conclusion

22. Circular Dichroism