Photoswitchable Nonlinear-Optical Crystal Based on a Dysprosium-Iron Nitrosyl Metal Assembly

Nitrosyl metal complexes (M-NO), in which nitrosyl ligands are coordinated to transition-metal ions, have been studied from the viewpoints of physiological activity, catalytic activity, and photosensitivity. The structural flexibility and electric polarization of the nitrosyl ligand are attractive characteristics. Herein we show a photoswitchable nonlinear-optical (NLO) crystal based on a dysprosium-iron nitrosyl assembly. This crystal is composed of a one-dimensional chain structure in the polar Pna2₁ space group. Because of spontaneous electric polarization, it exhibits a NLO effect of second harmonic generation (SHG). The SHG signal reversibly changes by alternate irradiation with 473 and 804 nm laser lights. The observed photoreversible switching effect on SHG is caused by photoinduced linkage isomerization of the metal nitrosyl sites, i.e., M-N⁺═O ↔ M-O═N⁺. Such an optically switchable NLO crystal should be useful for optical devices such as optical filters and optical shutters as well as probes in SHG microscopy.