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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• 作者：Korey P. Carter ; Kara E. Thomas ; Simon J. A. Pope ; Rebecca J. Holmberg ; Ray J. Butcher ; Muralee Murugesu ; Christopher L. Cahill
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：July 18, 2016
• 年：2016
• 卷：55
• 期：14
• 页码：6902-6915
• 全文大小：938K
• 年卷期：0
• ISSN：1520-510X

文摘

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.