Self-assembled Structure of Inorganic–Organic Hybrid Crystals Based on Keggin Polyoxometallates [SMo12O402–] and Supramolecular Cations

• DOI: 10.1021/acs.cgd.5b01388
• Publication Date: 2016-01-04T17:00:46Z
• Authors: Jun Xiong; Kazuya Kubo; Shin-ichiro Noro; Tomoyuki Akutagawa; Takayoshi Nakamura
• Keywords: 18-Crown-6; Divalent; Antiparallel (mathematics)

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