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Supramolecular assembly of molecular rare-earth–3,5-dichlorobenzoic acid–2,2′:6′,2″-terpyridine materials: structural systematics, luminescence properties, and magnetic behavior

Carter, Korey P., Thomas, Kara E., Pope, Simon J. A. ORCID: https://orcid.org/0000-0001-9110-9711, Holmberg, Rebecca J., Butcher, Ray J., Murugesu, Muralee and Cahill, Christopher L. 2016. Supramolecular assembly of molecular rare-earth–3,5-dichlorobenzoic acid–2,2′:6′,2″-terpyridine materials: structural systematics, luminescence properties, and magnetic behavior. Inorganic Chemistry 55 (14) , pp. 6902-6915. 10.1021/acs.inorgchem.6b00408

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Abstract

The syntheses and crystal structures of 16 new rare-earth (RE = La3+–Y3+)–3,5-dichlorobenzoic acid–terpyridine molecular materials characterized via single-crystal and powder X-ray diffraction are reported. These 16 complexes consist of four unique structure types ranging from molecular dimers (La3+ and Ce3+) to tetramers (Pr3+–Y3+) as one moves across the RE3+ series. This structural evolution is accompanied by subsequent changes in modes of supramolecular assembly (halogen bonding, halogen−π, halogen–halogen, and π–π interactions). Solid-state visible and near-infrared lifetime measurements were performed on complexes 6 (Sm3+), 7 (Eu3+), 9 (Tb3+), 10 (Dy3+), 11 (Ho3+), 12 (Er3+), and 14 (Yb3+), and characteristic emission was observed for all complexes except 11. Lifetime data for 11, 12, and 14 suggest sensitization by the terpy antenna does occur in near-infrared systems, although not as efficiently as in the visible region. Additionally, direct current magnetic susceptibility measurements were taken for complexes 10 (Dy3+) and 12 (Er3+) and showed dominant ferromagnetic behavior.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Additional Information: PDF uploaded in accordance with publisher's policies at http://www.sherpa.ac.uk/romeo/issn/0020-1669/ (30.6.16).
Publisher: American Chemical Society
ISSN: 0020-1669
Date of First Compliant Deposit: 28 June 2016
Date of Acceptance: 27 June 2016
Last Modified: 06 Nov 2023 18:57
URI: https://orca.cardiff.ac.uk/id/eprint/92169

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