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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

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journal contribution
posted on 27.06.2016, 17:48 by Korey P. Carter, Kara E. Thomas, Simon J. A. Pope, Rebecca J. Holmberg, Ray J. Butcher, Muralee Murugesu, Christopher L. Cahill
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.