TY - JOUR
T1 - Probing the Self-Assembly Mechanism of Lanthanide-Containing Sandwich-Type Silicotungstates [{Ln(H2O)n}2{Mn4(B-α-SiW9O34)2(H2O)2}]6- Using Time-Resolved Mass Spectrometry and X-ray Crystallography
AU - Fan, Lin Yuan
AU - Lin, Zheng Guo
AU - Cao, Jie
AU - Hu, Chang Wen
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/3/21
Y1 - 2016/3/21
N2 - The reaction of [γ-SiW10O36]8- with Mn2+ and Ln3+ in an aqueous solution led to the isolation of a series of new lanthanide-containing sandwich-type polyoxometalates (POMs) [{Ln(H2O)n}2{Mn4(B-α-SiW9O34)2(H2O)2}]6- (1-5a) (Ln = La (1), Nd (2), Gd (3), Dy (4), Er (5); n = 5, 6), which crystallize in the space groups C2/c with a = 33.0900(2)-32.9838(15) Å, b = 12.8044(10)-12.7526(6) Å, c = 22.8273(17)-22.6368(11) Å, V = 9669.2(12)-9519.7(8) Å3, Z = 2 (1, 2); P1¯ with a = 11.9502(4)-11.8447(6) Å, b = 13.2203(4)-13.1164(5) Å, c = 15.8291(5)-15.8524(7) Å, V = 2221.25(13)-2189.95(18) Å3, Z = 1 (3, 4, 5), respectively. X-ray diffraction analysis reveals that they consist of two-dimensional networks based on a sandwich-type polyanion [Mn4(B-α-SiW9O34)2(H2O)2]12- (6a, {Mn4(SiW9)2}) and lanthanide cations (Ln3+), which are further connected into three-dimensional frameworks by potassium cations for 3, 4, and 5. The unprecedented combination of time-resolved electrospray ionization mass spectrometry (ESI-MS) studies and X-ray crystallography allows us not only to directly observe the in-solution rearrangement of divant anion [γ-SiW10O36]8- into the sandwich-type POM 6a via an intermediate species [Mn3(B-β-SiW8O30(OH))(B-β-SiW9O33(OH))(H2O)]12- (7a, {Mn3(SiW8)(SiW9)}) from ESI-MS results, but also to gain the solid-state structures of intermediate and final product isolated from reaction solutions from X-ray crystallography results, from which the self-assembly mechanism of the lanthanide-containing sandwich-type POMs 1-5a was proposed.
AB - The reaction of [γ-SiW10O36]8- with Mn2+ and Ln3+ in an aqueous solution led to the isolation of a series of new lanthanide-containing sandwich-type polyoxometalates (POMs) [{Ln(H2O)n}2{Mn4(B-α-SiW9O34)2(H2O)2}]6- (1-5a) (Ln = La (1), Nd (2), Gd (3), Dy (4), Er (5); n = 5, 6), which crystallize in the space groups C2/c with a = 33.0900(2)-32.9838(15) Å, b = 12.8044(10)-12.7526(6) Å, c = 22.8273(17)-22.6368(11) Å, V = 9669.2(12)-9519.7(8) Å3, Z = 2 (1, 2); P1¯ with a = 11.9502(4)-11.8447(6) Å, b = 13.2203(4)-13.1164(5) Å, c = 15.8291(5)-15.8524(7) Å, V = 2221.25(13)-2189.95(18) Å3, Z = 1 (3, 4, 5), respectively. X-ray diffraction analysis reveals that they consist of two-dimensional networks based on a sandwich-type polyanion [Mn4(B-α-SiW9O34)2(H2O)2]12- (6a, {Mn4(SiW9)2}) and lanthanide cations (Ln3+), which are further connected into three-dimensional frameworks by potassium cations for 3, 4, and 5. The unprecedented combination of time-resolved electrospray ionization mass spectrometry (ESI-MS) studies and X-ray crystallography allows us not only to directly observe the in-solution rearrangement of divant anion [γ-SiW10O36]8- into the sandwich-type POM 6a via an intermediate species [Mn3(B-β-SiW8O30(OH))(B-β-SiW9O33(OH))(H2O)]12- (7a, {Mn3(SiW8)(SiW9)}) from ESI-MS results, but also to gain the solid-state structures of intermediate and final product isolated from reaction solutions from X-ray crystallography results, from which the self-assembly mechanism of the lanthanide-containing sandwich-type POMs 1-5a was proposed.
UR - https://www.scopus.com/pages/publications/84961751370
U2 - 10.1021/acs.inorgchem.5b02800
DO - 10.1021/acs.inorgchem.5b02800
M3 - Article
AN - SCOPUS:84961751370
SN - 0020-1669
VL - 55
SP - 2900
EP - 2908
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 6
ER -