Convenient crystal growth, structural determination and magnetic studies of layered copper hydroxides containing aromatic sulfonates. Issue 47 (11th November 2015)

• Record Type: Journal Article
• Authors: Fujita, Wataru
• Is Part Of: CrystEngComm. Volume 17:Issue 47(2015)
• Page Start: 9193
• Page End: 9202
• Publication Date: 2015-11-11
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/c5ce01731a
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : Single crystals of layered copper hydroxides containing some organic sulfonate anions were obtained by hydrolysis of acetate. Crystal structure determination and magnetic measurements of these materials were carried out. Abstract : Single crystals of layered copper hydroxides, 1–4, with aromatic sulfonate ions, p -toluenesulfonate, p -ethylbenzenesulfonate, 1-naphthalenesulfonate and 1, 5-naphthalenedisulfonate, respectively, were conveniently prepared by hydrolysis of aqueous copper acetate solutions containing the organic sulfonates. X-ray structure analyses revealed that these compounds had alternating stacks of copper hydroxide layers and aggregated layers of the organic ions. The atomic alignment of their copper hydroxide layers was similar to that of the inorganic layer of hydrotalcite, [Mg6 Al2 (OH)16 ]·CO3 ·16H2 O. However, their copper hydroxide layers were not isostructural among1–4 . In the copper hydroxide layers, not only hydroxide ions but also water molecules, acetate ions or the organic sulfonate ions were coordinated to the copper ions. The copper ions exhibited an elongated octahedral geometry in1 and2, and an elongated octahedral or square pyramidal geometry in3 and4 . The organic ions formed a bilayer arrangement in1 and2, and a monolayer arrangement in3 and4 . Magnetic measurements revealed primarily antiferromagnetic interactions between neighbouring copper ions. The magnetic behaviours of these materials resembled the antiferromagnetic ordering behaviour at low temperatures. The maximum values of χ p were observed at 3.8 K, 3.5 K, 3.2 K and 9.1 K for1–4, respectively. The exchange coupling constants were estimated from an S = 1/2 Heisenberg model with a two-dimensional triangular lattice magnetic network, where J / k B = 42.2 K, 36.8 K, 80.1 K and 84.9 K for1–4, respectively. The magnetic differences in these materials are due to the structural differences in their copper hydroxide layers. Thus, it was demonstrated that hydrolysis methods are suitable for the preparation of single crystals of various copper hydroxide derivatives with organic anions.