Self-assembled Structure of Inorganic–Organic Hybrid Crystals Based on Keggin Polyoxometallates [SMo12O402–] and Supramolecular Cations
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- 作者：Jun Xiong ; Kazuya Kubo ; Shin-ichiro Noro ; Tomoyuki Akutagawa ; Takayoshi Nakamura
- 刊名：Crystal Growth & Design
- 出版年：2016
- 出版时间：February 3, 2016
- 年：2016
- 卷：16
- 期：2
- 页码：800-807
- 全文大小：673K
- ISSN：1528-7505
文摘
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[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), and [(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 were characterized according to the size and charge of the supramolecular cations. In 1–4, two adjacent supramolecular cations ([(m-XAni+)(B[18]crown-6)]) were connected through π···π interactions forming sandwich-type dimers with the cations that were stacked in an antiparallel manner. In 8, DB[30]crown-10 included two cations constructing a larger divalent supramolecular cation [(3-F-4-MeAni+)2(DB[30]crown-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 B[18]crown-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.