Hollow Superhelices Based on Chiral Europium Coordination Polymers

The construction of helical nanotubes based on chiral coordination polymers (CPs) is an intriguing but challenging task, which is important for the development of functional materials that combine macroscopic chirality with tube-related properties. Here, we selected a chiral europium phosphonate system, e. g., Eu(NO₃)₃/R-,S-pempH₂, and carried out a systematic work. By controlling the hydrothermal reaction conditions such as the pH value of the reaction mixture, the molar ratio and concentration of the reactants, we obtained block-like crystals of R/S-1 b, rod-like crystals of R/S-3 r, hollow superhelices of R/S-2 hh, and solid superhelices of R/S-4 sh. In the latter two cases, the chirality has been successfully transferred and amplificated from the molecular level to the macroscopic level. Interestingly, compounds R/S-2 hh and R/S-4 sh have the same chemical composition of Eu(R/S-pempH)₃⋅2H₂O and show identical PXRD patterns, thus can be considered as the same material except for different morphologies. We further investigated their circularly polarized luminescence (CPL) properties and found that the hollow superhelix of R/S-2 hh had a larger dissymmetry factor than the solid superhelix of R/S-4 sh. This study not only provides the first example of hollow superhelices of chiral CPs, but also offers the possibility of modulating the chiroptical properties of CPs through morphological control.