%0 Generic
%A Fan, Lin-Yuan
%A Lin, Zheng-Guo
%A Cao, Jie
%A Hu, Chang-Wen
%D 2016
%T 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
%U https://acs.figshare.com/articles/dataset/Probing_the_Self_Assembly_Mechanism_of_Lanthanide_Containing_Sandwich_Type_Silicotungstates_Ln_H_sub_2_sub_O_sub_i_n_i_sub_sub_2_sub_Mn_sub_4_sub_B_SiW_sub_9_sub_O_sub_34_sub_sub_2_sub_H_sub_2_sub_O_sub_2_sub_sup_6_sup_Using_Time_Resolved_Mass_Spectrometr/3102844
%R 10.1021/acs.inorgchem.5b02800.s007
%2 https://ndownloader.figshare.com/files/4823545
%K potassium cations
%K reaction solutions
%K 10O
%K POM 6
%K Mn
%K lanthanide cations
%K Ln
%K crystallography
%K SiW
%X 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); P1̅
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.
%I ACS Publications