A Large Family of Centrosymmetric and Chiral f-Element-Bearing Iodate Selenates Exhibiting Coordination Number and Dimensional Reductions.

The exploration of phase formation in the f-element-bearing iodate selenate system has resulted in 14 novel rare-earth-containing iodate selenates, Ln(IO)(SeO) (Ln = La, Ce, Pr, Nd; LnISeO-1), Ln(IO)(SeO)(HO) (Ln = Sm, Eu; LnISeO-2), and Ln(IO)(SeO)(HO)·HO (Ln = Gd, Dy, Ho, Er, Tm, Yb, Lu, Y; LnISeO-3), as well as two new thorium iodate selenates, Th(OH)(IO)(SeO)(HO) (ThISeO-1) and Th(IO)(SeO) (ThISeO-2). LnISeO-3 and ThISeO-2 crystallize in the chiral space group P222, while LnISeO-1, LnISeO-2, and ThISeO-1 crystallize in the centrosymmetric space group P2/c. The numbers of both coordinating and hydrating water molecules crystallized in LnISeO-1, LnISeO-2, and LnISeO-3 increase along these three series, in line with the increasingly negative values of hydration enthalpies of heavier trivalent lanthanide ions. Such a systematic change in compositions, especially the first coordination sphere of Ln, further induces structural rearrangements, including coordination number and dimensional reductions. More specifically, the structures of LnISeO-1, LnISeO-2, and LnISeO-3 have undergone transitions from 2D Ln-oxo layers with 10-coordinate Ln centers to 1D Ln-oxo chains with 9-coordinate Ln centers and then to 0D Ln-oxo monomers with 8-coordinate Ln centers, respectively. The formation and characterization of this large family of Ln/Th iodate selenates suggest that such a mixed-anion system not only exhibits richer structural chemistry but also can be capable of generating intriguing properties, such as the second-harmonic generation (SHG) effect.