Nitrophenolate as a Building Block for Lanthanide Chains, Layers, and Clusters

Abstract

Potassium o-nitrophenolate (1) was reacted with various lanthanide trichlorides under different reaction conditions. By using the smaller lanthanides and working under rigorous exclusion of air, infinite chains of composition [(THF)4[K(o-O2N-C6H4-O)4Ln]4]n (Ln = Y (2a), Er (2b), Lu (2c)) were obtained. Using the same conditions but performing the crystallization under air, tetradecanuclear clusters of composition H18[Ln14(micro-eta2-o-O2N-C6H4-O)8(eta2-o-O2N-C6H4-O)16(micro4-O)2(micro3-O)16] (Ln = Dy (3a), Er (3b), Tm (3c), Yb (3d)) were isolated. Using larger center metals such as samarium, europium, and terbium and working under rigorous exclusion of air, infinite layers of composition [[K2(o-O2N-C6H4-O)5Tb]n] (4) and [[K2(o-O2N-C6H4-O)5Ln)]n] (Ln = Sm (5a), Eu (5b)) were obtained. In 4 the layers have a closer packing than those in compound 5. The closer packing is a result of the increased coordination number of the lanthanide metal and the potassium atoms. In contrast, the more open structures of 5 results in channels which are rectangular through the layers. All compounds reported including 1 have been investigated by single-crystal X-ray diffraction.