RE(OH)2NO3 (RE = Tb, Dy, Ho, and Er): Synthesis and Nonlinear Optical Properties of Water-Resistant Lanthanide Hydroxide Nitrates

A series of lanthanide-containing water-resistant nitrates, namely RE(OH)2NO3 (RE = Tb(1), Dy(2), Ho(3), and Er(4)), was obtained through the hydrothermal process. As possible nonlinear optical materials, they feature a layered isomorph composed of an [REO3(OH)6] polyhedron and an [NO3] triangle, and the synergistic arrangement of the [REO3(OH)6] and [NO3] groups in their structures leads to their obvious second-order nonlinear optical effect. Nevertheless, the unique optical absorption caused by the electronic transitions on 4f-4f orbitals of lanthanides results in their second harmonic generation responses of different strengths, with 1 exhibiting 5.07 times that of KDP, but 2-4 showing less than half of KDP. In addition, 1 possesses an outstanding water-resistant capacity and a transparent cut-off edge around 300 nm, foreshadowing its potential value as a nonlinear optical crystal. Moreover, 1 is found to emit characteristic green fluorescence due to the typical 5D4 → 7F5 transitions of the excited Tb3+ ions.