Postsynthetic Modification of NU-1000 for Designing a Polyoxometalate-Containing Nanocomposite with Enhanced Third-Order Nonlinear Optical Performance

Abstract

For the advancement of laser technologies and optical engineering, various types of new inorganic and organic materials are emerging. Metal-organic frameworks (MOFs) reveal a promising use in nonlinear optics, given the presence of organic linkers, metal cluster nodes, and possible delocalization of π-electron systems. These properties can be further enhanced by the inclusion of solely inorganic materials such as polyoxometalates as prospective low-cost electron-acceptor species. In this study, a novel hybrid nanocomposite, namely, SiW₁₂@NU-1000 composed of SiW₁₂ (H₄SiW₁₂O₄₀) and Zr-based MOF (NU-1000), was assembled, completely characterized, and thoroughly investigated in terms of its nonlinear optical (NLO) performance. The third-order NLO behavior of the developed system was assessed by <i>Z</i>-scan measurements using a 532 nm laser. The effect of two-photon absorption and self-focusing was significant in both NU-1000 and SiW₁₂@NU-1000. Experimental studies suggested a much superior NLO performance of SiW₁₂@NU-1000 if compared to that of NU-1000, which can be assigned to the charge-energy transfer between SiW₁₂ and NU-1000. Negligible light scattering, good stability, and facile postsynthetic fabrication method can promote the applicability of the SiW₁₂@NU-1000 nanocomposite for various optoelectronic purposes. This research may thus open new horizons to improve and enhance the NLO performance of MOF-based materials through π-electron delocalization and compositing metal-organic networks with inorganic molecules as electron acceptors, paving the way for the generation of novel types of hybrid materials for prospective NLO applications.