Polarized Laser Switching with Giant Contrast in MOF-Based Mixed-Matrix Membrane

Nonlinear optical (NLO) switch materials have attracted considerable attention in photonics. Although various materials based on complex structural transitions have been developed extensively, the studies on light-driven up-conversion laser switches are rare, which have advantages including easy operations at room temperature and high contrasts. Here, the concept of photoswitch building unit is proposed to construct a novel sandwich-like mixed-matrix membrane. Dye@metal-organic framework (MOF) crystals and spirooxazine are regarded as the laser emission and absorption units, followed by their hierarchical encapsulation into the polydimethylsiloxane carrier unit. Excited MOF microcrystals exhibit two-photon pumped lasing anisotropy, with an ultrahigh degree of linear polarization (≈99.9%). Photochromic molecules can be interconverted by the external ultraviolet stimulus, causing sharp absorption-band variations and inducing the laser emission or quenching. Such up-conversion polarized laser switch material is reported for the first time. Record-high NLO contrast (≈6.1 × 10⁴ ) among the solid-state NLO switch materials can be obtained through simultaneously controlling the ultraviolet irradiation and the emission-detected polarization direction at room temperature.