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

Abstract

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 sandwi...