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RE-Halobenzoic Acid-Terpyridine Complexes, Part V: Synthesis and Supramolecular Assembly of Rare-Earth-3,5-Dihalobenzoic Acid-Terpyridine Materials and Subsequent Comparison of Non-covalent Interactions

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Abstract

The synthesis and crystal structures of 48 new rare-earth (RE = La3+—Y3+)-3,5-dihalogenated benzoic acid (3,5-dibromobenzoic acid [3,5-dBrBA] and 3-bromo-5-iodobenzoic acid [3,5-BrIBA])-terpyridine [TPY] complexes are reported. Ligand based supramolecular assembly drives the formation of five distinct structure types across the lanthanide series. Featured in these structures are multiple significant halogen bonding interactions occurring at the terminal halide substituents in the form of halogen–halogen, halogen–oxygen, and halogen–π interactions. This series complements previous efforts to synthesize and evaluate a catalogue of Ln-halobenzoic acid-TPY materials. With these data, a comparison of the influence of halogen interactions on supramolecular assembly is provided. As one might expect, the frequency with which halogen bonding occurs and the displacement of other assembly mechanisms, depends on the number and polarizability of the halogen species. Structures across these series fall into multiple distinct structure types, as defined by tecton geometry. Since these tectons are isostructural across each respective series, trends in halogen bond propensity can be derived. In this comparison, the likelihood of halogen bonding and disruption of π–π stacking is shown to increase as halogen size increases.

Graphic Abstract

Two new series of rare-earth (RE = La3+–Y3+)-3,5-dihalogenated benzoic acid (3,5-dibromobenzoic acid and 3-bromo-5-iodobenzoic acid)-terpyridine complexes are synthesized and compared, with respect to supramolecular assembly, to each other and previously reported RE-halogenated benzoic acid-terpyridine series in order to study the role of halogen bonding in this system.

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Acknowledgements

This work was supported internally by the Chemistry Department and the Columbian College of Arts and Sciences at The George Washington University. We would like to acknowledge the staff and instructors of American Crystallographic Association’s Summer Course in Chemical Crystallography (Summer 2019, Northwestern University, Evanston IL) for assistance in data collection and structure determination for select complexes presented in this paper. Finally, the authors are indebted to Mr. Gareth Nicholas (Haverford College) for synthesis efforts during a summer internship at GW.

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  1. Department of Chemistry, The George Washington University, 800 22nd Street, NW, Washington, DC, 20052, USA

    Jordan A. Herder, Benjamin W. Walusiak & Christopher L. Cahill

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  1. Jordan A. Herder
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  2. Benjamin W. Walusiak
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  3. Christopher L. Cahill
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Correspondence to Christopher L. Cahill.

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Unit cell parameters, data quality statistics and CCDC reference codes of all crystal structures are included in the electronic supplementary material.

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Herder, J.A., Walusiak, B.W. & Cahill, C.L. RE-Halobenzoic Acid-Terpyridine Complexes, Part V: Synthesis and Supramolecular Assembly of Rare-Earth-3,5-Dihalobenzoic Acid-Terpyridine Materials and Subsequent Comparison of Non-covalent Interactions. J Chem Crystallogr 51, 317–336 (2021). https://doi.org/10.1007/s10870-020-00858-x

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