Find research datasets worth reusing

Noncentrosymmetric Lanthanide-Based MOF Materials Exhibiting Strong SHG Activity and NIR Luminescence of Er3+: Application in Nonlinear Optical Thermometry

<p>Optically active luminescent materials based on lanthanide ions attract significant attention due to their unique spectroscopic properties, nonlinear optical activity, and the possibility of application as contactless sensors. Lanthanide metal-organic frameworks (Ln-MOFs) that exhibit strong second-harmonic generation (SHG) and are optically active in the NIR region are unexpectedly underrepresented. Moreover, such Ln-MOFs require ligands that are chiral and/or need multistep synthetic procedures. Here, we show that the NIR pulsed laser irradiation of the noncentrosymmetric, isostructural Ln-MOF materials (MOF-Er³⁺ (1) and codoped MOF-Yb³⁺/Er³⁺ (2)) that are constructed from simple, achiral organic substrates in a one-step procedure results in strong and tunable SHG activity. The SHG signals could be easily collected, exciting the materials in a broad NIR spectral range, from &asymp;800 to 1500 nm, resulting in the intense color of emission, observed in the entire visible spectral region. Moreover, upon excitation in the range of &asymp;900 to 1025 nm, the materials also exhibit the NIR luminescence of Er³⁺ ions, centered at &asymp;1550 nm. The use of a 975 nm pulse excitation allows simultaneous observations of the conventional NIR emission of Er³⁺ and the SHG signal, altogether tuned by the composition of the Ln-MOF materials. Taking the benefits of different thermal responses of the mentioned effects, we have developed a nonlinear optical thermometer based on lanthanide-MOF materials. In this system, the SHG signal decreases with temperature, whereas the NIR emission band of Er³⁺ slightly broadens, allowing ratiometric (Er³⁺ NIR 1550 nm/SHG 488 nm) temperature monitoring. Our study provides a groundwork for the rational design of readily available and self-monitoring NLO-active Ln-MOFs with the desired optical and electronic properties.</p>