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. ORCID: https://orcid.org/0000-0001-9110-9711, 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:	26 Nov 2024 16:45
URI:	https://orca.cardiff.ac.uk/id/eprint/107829

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