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

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(μ-η2-o-O2N-C6H4-O)8(η2-o-O2N-C6H4-O)16(μ4-O)2(μ3-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.