Ultraviolet Nonlinear Optical Single Crystals of A Three-Dimensional Chiral Covalent Framework Containing Te−O−B−O Bonds

Extending covalent organic frameworks (COFs) into crystalline carbon-free covalent backbones is an important strategy to endow these materials with more exotic functions. Integrating metal-free inorganic and organic components into one covalent framework is an effective way to address the issue of poor thermal/solvent stability in the field of nonlinear optics (NLO). However, constructing such structures is very challenging. Here, we linked 3-connected nods (BO₃) and 2-connected organic building blocks (Te(Ph)₂) together to produce colorless single crystals (size up to 400 μm) of a three-dimensional (3D) chiral covalent framework (CityU-22). The single-crystal X-ray diffraction (SCXRD) analysis reveals that CityU-22 has a non-carbon Te−O−B−O bond-based network with the srs topology. The chiral CityU-22 displays good stability under the treatment of different common solvents or heat (the decomposition temperature above 300 °C). Due to its non-π-conjugated backbone (−Te−O−B−O−), CityU-22 shows an ultraviolet NLO behavior with a second-harmonic generation (SHG) response similar to KH₂PO₄ (KDP).