TY - JOUR
T1 - A Large Family of Centrosymmetric and Chiral f-Element-Bearing Iodate Selenates Exhibiting Coordination Number and Dimensional Reductions
AU - Qie, Meiying
AU - Lin, Jian
AU - Kong, Fang
AU - Silver, Mark A.
AU - Yue, Zenghui
AU - Wang, Xiaomei
AU - Zhang, Linjuan
AU - Bao, Hongliang
AU - Albrecht-Schmitt, Thomas E.
AU - Wang, Jian Qiang
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/2/5
Y1 - 2018/2/5
N2 - The exploration of phase formation in the f-element-bearing iodate selenate system has resulted in 14 novel rare-earth-containing iodate selenates, Ln(IO3)(SeO4) (Ln = La, Ce, Pr, Nd; LnISeO-1), Ln(IO3)(SeO4)(H2O) (Ln = Sm, Eu; LnISeO-2), and Ln(IO3)(SeO4)(H2O)2·H2O (Ln = Gd, Dy, Ho, Er, Tm, Yb, Lu, Y; LnISeO-3), as well as two new thorium iodate selenates, Th(OH)(IO3)(SeO4)(H2O) (ThISeO-1) and Th(IO3)2(SeO4) (ThISeO-2). LnISeO-3 and ThISeO-2 crystallize in the chiral space group P212121, while LnISeO-1, LnISeO-2, and ThISeO-1 crystallize in the centrosymmetric space group P21/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.
AB - The exploration of phase formation in the f-element-bearing iodate selenate system has resulted in 14 novel rare-earth-containing iodate selenates, Ln(IO3)(SeO4) (Ln = La, Ce, Pr, Nd; LnISeO-1), Ln(IO3)(SeO4)(H2O) (Ln = Sm, Eu; LnISeO-2), and Ln(IO3)(SeO4)(H2O)2·H2O (Ln = Gd, Dy, Ho, Er, Tm, Yb, Lu, Y; LnISeO-3), as well as two new thorium iodate selenates, Th(OH)(IO3)(SeO4)(H2O) (ThISeO-1) and Th(IO3)2(SeO4) (ThISeO-2). LnISeO-3 and ThISeO-2 crystallize in the chiral space group P212121, while LnISeO-1, LnISeO-2, and ThISeO-1 crystallize in the centrosymmetric space group P21/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.
UR - https://www.scopus.com/pages/publications/85041638561
U2 - 10.1021/acs.inorgchem.7b03116
DO - 10.1021/acs.inorgchem.7b03116
M3 - 文章
C2 - 29345469
AN - SCOPUS:85041638561
SN - 0020-1669
VL - 57
SP - 1676
EP - 1683
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 3
ER -