RE-Halobenzoic Acid-Terpyridine Complexes, Part V: Synthesis and Supramolecular Assembly of Rare-Earth-3,5-Dihalobenzoic
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ORIGINAL PAPER
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 Jordan A. Herder1 · Benjamin W. Walusiak1 · Christopher L. Cahill1 Received: 11 June 2020 / Accepted: 20 August 2020 © Springer Science+Business Media, LLC, part of Springer Nature 2020
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-bromo5-iodobenzoic acid)-terpyridine complexes are synthesized and compared, with respect to supramolecular assembly, to each
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s10870-020-00858-x) contains supplementary material, which is available to authorized users. * Christopher L. Cahill [email protected] 1
Department of Chemistry, The George Washington University, 800 22nd Street, NW, Washington, DC 20052, USA
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Journal of Chemical Crystallography
other and previously reported RE-halogenated benzoic acid-terpyridine series in order to study the role of halogen bonding in this system.
Keywords Lanthanides · Crystal structure · Supramolecular assembly · Halogen bonding
Introduction Rare-earth (RE) materials in general have been studied extensively due to their unique applications for luminescence, photon upconversion, and sensing [1]. A large coordination number, typically 6–12, provides a diverse array of possibilities for modification of the ligand binding of these elements. Control of the immediate coordination environment of lanthanides is essential to retain their desirable properties and enab
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