Application of temperature-controlled chiral hybrid structures constructed from copper(ii)-monosubstituted Keggin polyoxoanions and copper(ii)-organoamine complexes in enantioselective sensing of tartaric acid

Abstract

Temperature usually occupies a crucial position in the construction of chiral compounds. By controlling the temperature of the reaction system, chiral and non-chiral compounds can be designed and synthesized. Given the above, three new chiral and non-chiral compounds based on copper(II) monosubstituted polyoxoanions and Cu(en) complexes (en = ethylenediamine), D/L-[Cu(H₂O)(en)₂]₂{[Cu(H₂O)₂(en)][SiCuW₁₁O₃₉]}·5H₂O (1, D-1 and L-1) and [Cu(H₂O)(en)₂]{[Cu(en)₂]₂[SiCuW₁₁O₃₉]}·2.5H₂O (2), were successfully synthesized under hydrothermal conditions. The main synthesis conditions of compound 1 (D-1 and L-1) and compound 2 are the same, however, the only difference is that the reaction temperatures are 80 °C and 140 °C, respectively. What's more, compounds 1 and 2 can form a 1D chiral chain by Cu–O and W/Cu–O–W/Cu bonds, respectively, and further obtain a 3D-supramolecular framework through hydrogen bonding interaction. Meanwhile, due to the asymmetry of chiral compound 1, optical second-harmonic generation (SHG) was used to investigate the second-order nonlinear optical effect and it was found that the observed SHG efficiency of compound 1 is 0.3 times that of urea. To further investigate the chiral properties, D-1 and L-1 were used in the electrochemical enantioselective sensing of D-/L-tartaric acid (D-/L-tart) molecules, respectively, which demonstrates that D-1 and L-1 have a good application prospect in sensing chiral substances.