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+)(Bcrown-6)]2[SMo12O402-] (Ani+ = anilinium; Bcrown-6 = benzocrown-6; X = F (1), Cl (2), Br (3), or I (4)), [(4-MeAni+)(Bcrown-6)]2[SMo12O402-]·CH3CN (5), [(4-MeAni+)(DBcrown-6)]2[SMo12O402-]·2CH3CN (6), [(3-F-4-MeAni+)(DBcrown-6)]2[SMo12O402-]·2CH3CN (7), and [(3-F-4-MeAni+)2(DBcrown-10)][SMo12O402-]·2CH3CN (8) (4-MeAni+ = 4-methylanilinium; DBcrown-6 = dibenzocrown-6; 3-F-4-MeAni+ = 3-fluoro-4-methylanilinium; DBcrown-10 = dibenzocrown-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+)(Bcrown-6)]) were connected through π⋯π interactions forming sandwich-type dimers with the cations that were stacked in an antiparallel manner. In 8, DBcrown-10 included two cations constructing a larger divalent supramolecular cation [(3-F-4-MeAni+)2(DBcrown-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 π⋯π stacking interaction was present in the adjacent Bcrown-6. Monovalent supramolecular cations were present in 5-7 with a ratio of 1:2 between [SMo12O402-] and the supramolecular cations. The supramolecular cations formed hexagonal-assembled structures.
ASJC Scopus subject areas
- 化学 (全般)