Naphthopyran-Based Silica Nanoparticles as New High-Performance Photoresponsive Materials.

Hybrid nanomaterials based on the covalent grafting of silylated naphthopyrans (NPTs) onto silica nanoparticles (SiO2 NPs) were successfully prepared and studied as new photochromic materials. They were prepared by a two-step protocol consisting of (i) NPTs (derivatives from 2H-naphtho[1,2-b]pyran (2H-NPT) and 3H-naphtho[2,1-b]pyran (3H-NPT)) silylation by a microwave-assisted reaction between hydroxyl-substituted NPTs and 3-(triethoxysilyl)propyl isocyanate, followed by (ii) covalent post-grafting onto SiO2 NPs. In order to study the role of the silylation step, the analogous non-silylated nanomaterials were also prepared by direct adsorption of NPTs. The characterization techniques confirmed the successful NPTs silylation and subsequent grafting to SiO2 NPs. All SiO2-based nanomaterials revealed photoswitching behavior, following a biexponential decay. The SiO2 NPs functionalized with silylated 3H-NPTs (SiO2@S3 and SiO2@S4) presented the most promising photochromic properties, showing fast coloration/decoloration kinetics (coloring in 1 min under UV irradiation and fading in only 2 min) and high values of total color difference (ΔE*ab = 30-50). Also, the 2H-NPTs-based SiO2 NPs (SiO2@S1 and SiO2@S2) presented fast coloration and good color contrasts (ΔE*ab = 54), but slower fading kinetic rates, taking more than 2 h to return to their initial color. In contrast, the SiO2 NPs functionalized with non-silylated NPTs (SiO2@1 and SiO2@3) showed weaker color contrasts (ΔE*ab = 6-10) and slower fading kinetics, proving that the NPT silylation step was crucial to enhance the photochromic behavior of SiO2 NPs based on NPTs. Furthermore, the silylated-based nanomaterials showed good photostability upon prolonged UV light exposure, keeping their photochromic performance unchanged for at least 12 successive UV/dark cycles, anticipating interesting technological applications in several areas.