Crystal structure or chemical composition of salt–sugar-based metal–organic frameworks: what are the nonlinear optical properties due to?

In the last few decades optical imaging techniques based on nonlinear optical properties have been of interest for biosensing applications. This work focuses on two isostructural and isomorphous sugar-derived metal–organic frameworks (MOFs) with second-harmonic generation (SHG) properties, in order to investigate their possible application as biosensors in view of their high biocompatibility. Combining 2-de­oxy-d-galactose with the metal halogenides CaX (2) (X = Br, I), two new isomorphous MOFs of formula [Ca(C(6)H(12)O(5))(2)]X (2) were obtained and characterized through single-crystal X-ray diffraction. The first-order static hyperpolarizability and second-order susceptibility were estimated by in vacuo and in-crystal density functional theory calculations, and compared with the experimental SHG response of powdered samples. The parameters influencing the SHG response of these compounds were investigated by comparison with similar previously analysed MOFs, to understand how to design more efficient materials to be used as nanoprobes by exploiting crystal engineering techniques.