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Exploring the promotion of synthons of choice: halogen bonding in molecular lanthanide complexes characterized via X-ray diffraction, luminescence spectroscopy, and magnetic measurements

Carter, Korey P., Pope, Simon J. A., Kalaj, Mark, Holmberg, Rebecca J., Murugesu, Muralee and Cahill, Christopher L. 2017. Exploring the promotion of synthons of choice: halogen bonding in molecular lanthanide complexes characterized via X-ray diffraction, luminescence spectroscopy, and magnetic measurements. Zeitschrift für ganische und allgemeine Chemie 643 (23) , pp. 1948-1955. 10.1002/zaac.201700341

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Abstract

Promotion of a synthon of choice for the non-covalent assembly of lanthanide tectons represents both a noteworthy challenge and opportunity within LnIII hybrid materials. We have developed a system, wherein some control can be exercised over supramolecular assembly and, as part of continued efforts to improve this process we have generated a family of ten new lanthanide (Ln = Sm3+ – Lu3+) 2,4,6-trichlorobenzoic acid-1,10-phenanthroline molecular complexes. Delineation of criteria for promoting assembly via halogen based interactions was introduced previously and is refined herein based on the characterization of complexes 1–10 via single-crystal X-ray diffraction. Direct comparison of means of supramolecular assembly for 1–10 with isostructural Ln-p-chlorobenzoic acid-1,10-phenanthroline analogues verifies that increasing the number of halogen atoms at the periphery of a tecton is one route that increases the frequency of halogen bonding interactions. Additionally, solid-state visible and near-IR photoluminescence and luminescent lifetime data were collected for complexes 1 (Sm3+), 2 (Eu3+), 4 (Tb3+), 5 (Dy3+), 6 (Ho3+), 7 (Er3+), and 9 (Yb3+) and characteristic emission was observed for all complexes except 6. Further, direct current magnetic susceptibility measurements were carried out for complexes 5 (Dy3+) and 7 (Er3+), and two slow magnetic relaxation processes were characterized using alternating current magnetic susceptibility measurements for 5.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: Wiley-Blackwell
ISSN: 0044-2313
Date of First Compliant Deposit: 2 January 2018
Date of Acceptance: 13 October 2017
Last Modified: 17 Oct 2018 03:15
URI: http://orca.cf.ac.uk/id/eprint/107829

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