Crystal growth, structures and magnetic properties of copper hydroxide compounds with distorted diamond chain magnetic networks

Abstract

Single crystals of copper hydroxide compounds (1-7) containing organic sulfonate ions (ethane-1,2disulfonate, 1-octanesulfonate, p-toluenesulfonate, p-ethylbenzenesulfonate, 2-naphthalenesulfonate, 1,5naphthalenedisulfonate, and 2,6-naphthalenedisulfonate, respectively) were easily prepared by the hydrolysis of copper acetate aqueous solution containing the respective organic sulfonates. All seven compounds had distorted diamond chain magnetic networks similar to that found in azurite (Cu 3 (CO 3 ) 2 (OH) 2 ). The diamond chain units were composed of copper, hydroxide, and acetate ions and water molecules (with additional sulfonate ions in the case of 7). The anions or molecules bridged the neighbouring copper ions, and might mediate superexchange interactions between copper atoms. The chain units did not have the same structure, and were slightly different in their Cu-O bond lengths, Cu-O-Cu bridging angles and so on.Magnetic measurements revealed primarily antiferromagnetic interactions between the neighbouring copper ions and no antiferromagnetic ordering. The χ p vs. T plots showed broad maxima at around 60-80 K that are characteristic of low-dimensional magnetic networks. Compounds 1-6 were paramagnetic down to 2 K, while 7 had a diamagnetic ground state. The different magnetic properties are due to the small structural differences in the diamond chain units, because the sign and intensity of magnetic coupling between the neighbouring copper ions are sensitive to the bridging structures. Copper hydroxide compounds with different organic ions and diverse structures prepared by this hydrolysis method will facilitate the systematic study of the underlying diamond chain magnetic networks.

Noncentrosymmetric Cu(II) Layered Hydroxide: Synthesis, Crystal Structure, Nonlinear Optical, and Magnetic Properties of Cu2(OH)3(C12H25SO4)

“…interactions. The curve presents a sharp maximum at 10.5 K with a very broad shoulder centered around 70 K. This peculiar shape, with two, more or less defined, peaks in  = f(T) has already been observed in other diamond-like Cu(II) hydroxide chains, with sulfonate and acetate ligands, 47 or for the related Cu3(OH)2(CO3)2 azurite. 48 The  = f(T) curve for 1 could be fitted above 7 K, considering isolated chains (separated by the long dodecylsulfate molecules), and the spin topology schematized on figure 8.…”

Frustrated magnetism of spin-1/2 Heisenberg diamond and octahedral chains as a statistical-mechanical monomer-dimer problem

“…In the present paper we will generalize the localizedmagnon theories established previously for the spin-1/2 Heisenberg diamond and octahedral chains by extending their validity to a less frustrated parameter space including dimer-tetramer [29] and tetramerhexamer [25] ground states, respectively. It is worthwhile to remark that the spin-1/2 Heisenberg diamond chain bears a close relation to several copper-based magnetic compounds such as azurite Cu 3 (CO 3 ) 2 (OH) 2 [30,31], A 3 Cu 3 AlO 2 (SO 4 ) 4 (A = K, Rb, and Cs) [32][33][34], [Cu 3 (OH) 2 (CH 3 COO)(H 2 O) 4 ](RSO 3 ) 2 (RSO 3 = organic sulfonate anions) [35] and Cu 3 (CH 3 COO) 4 (OH) 2 • 5H 2 O [36]. Although we do not have at present any knowledge about a possible experimental realization of the spin-1/2 Heisenberg octahedral chain a relatively numerous family of hexanuclear complexes with the magnetic core of a discrete copper-based octahedron {Cu 6 } [37][38][39][40] could be used for a brick-and-mortar synthesis of a one-dimensional copper polymeric chain of cornersharing octahedra.…”

Crystal structures, and magnetic and thermal properties of basic copper formates with two-dimensional triangular-lattice magnetic networks

“…Furthermore, copper hydroxides bearing organic sulfonate ions (RSO 3 − ) were successfully prepared by the hydrolysis of acetate ions, and these compounds were shown to exhibit two-dimensional triangular-lattice or diamond-chain-lattice magnetic networks. 12 In addition, Evrard et al recently reported the successful preparation of single crystals of copper hydroxides with the decanesulfate anion (A = n -C 12 H 25 SO 4 − ) by hydrolysis, and discussed their magnetic properties, among others. 13 The hydrolysis methods are useful for preparation of single crystals of metal hydroxides with various anions and will contribute structural chemistry of them.…”