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首页> 外文期刊>Crystal growth & design >Self-assembled Structure of Inorganic Organic Hybrid Crystals Based on Keggin Polyoxometallates SMo12O402- and Supramolecular Cations
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Self-assembled Structure of Inorganic Organic Hybrid Crystals Based on Keggin Polyoxometallates SMo12O402- and Supramolecular Cations

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摘要

To investigate the network structure of inorganic organic hybrid crystals, we synthesized a series of assemblies based on polyoxometallates (POMs) SMo12O402- and different supramolecular cations consisting of anilinium and crown ether derivatives. The compounds (m-XAni(+))(B-18crown-6)(2)SMo12O402- (Ani(+) = anilinium; B 18 crown-6 = benzo18crown-6; X = F (1), Cl (2), Br (3), or I (4)), (4-MeAn(+)) (B 18 crown-6)(2)SMo12O4020center dot CH3CN (5), (4-MeAni(+)) (DB 18 crown-6)(2)SMo12O402-center dot 2CH(3)CN (6), (3-F-4-MeAni(+)) (DB 18 crown-6)(2)SMo12O402-center dot 2CH(3)CN (7), and (3-F-4-MeAni(+))(2)(DB 30crown-10) SMo12O402-center dot 2CH(3)CN (8) (4-MeAni(+) = 4-methylanilinium; DB 18 crown-6 = dibenzo18crown-6; 3-F-4-MeAni = 3-fluoro-4-methylanilinium; DB30 crown-10 = dibenzo30crown-10) were synthesized. Their crystal architectures were characterized according to the size and charge of the supramolecular cations. In 1-4, two adjacent supramolecular cations ((m-XAni(+))(B18crown-6)) were connected through pi center dot center dot center dot pi interactions forming sandwich-type dimers with the cations that were stacked in an antiparallel manner. In 8, DB30 crown-10 included two cations constructing a larger divalent supramolecular cation (3-F-4-MeAni(+))(2)(DB30crown-10). In 1-4 and 8, the ratio between SMo12O402- and the supramolecular cations was 1:1, and the latter formed rectangular-assembled structures. In 5, the pi center dot center dot center dot pi stacking interaction was present in the adjacent B18crown-6. Monovalent supramolecular cations were present in 5-7 with a ratio of 1:2 between SMo(12)O4(02)(-) and the supramolecular cations. The supramolecular cations formed hexagonal-assembled structures.

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