Structural Complexity and Magnetic Orderings in a Large Family of 3d-4f Heterobimetallic Sulfates.

The synthesis of a large family of heterobimetallic lanthanide copper sulfates was realized via stoichiometric hydrothermal reactions among LnO, CuO, and HSO, giving rise to four distinct phases, namely LnCu(SO)(OH) (Ln = Sm-Ho) (), LnCu(SO)(OH) (Ln = Tm-Lu) (), LnCu(SO)(OH) (Ln = Nd-Gd, except Pm) (), and LnCu(SO)(OH) (Ln = Dy-Lu) (), with completely different topologies. The passage from and to and across the 4f series, respectively, can be ascribed to the effect of lanthanide contraction, which progressively induces shrinking of the Ln-O distance, reduction in the Ln coordination number, and eventually structural transitions. The incorporation of identical 3d-4f metal ions into different spin-lattices, in conjunction with substitution of diverse Ln cations within the same spin-lattice, gives rise to tunable magnetic properties varying from ferromagnetic ordering in and to antiferromagnetic ordering in , and to paramagnetic correlations found in and .