Polyanionic clusters embedded in lattice-type hydrogen bonding networks involving in situ bond activation and coupling of organic cationsElectronic supplementary information (ESI) available: Crystal CIF files, IR, XRD, 1H NMR spectra and other figures. CCDC 1405995 and 1405996. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5ce01220a

• Main Authors: Han, Zhan-Gang, Liu, Yun-Ping, Zhao, Xiao-Fang, Yan, Jin-Shuang, Zhai, Xue-Liang
• Format: Journal Article
• Language: English
• Published: 22.09.2015
• ISSN: 1466-8033
• DOI: 10.1039/c5ce01220a

Two inorganic-organic supramolecular polyoxometalates, (H 2 chtpy) 2 [SiW 12 O 40 ] ( 1 ) (chtpy = 1,3,4,6-tetra(4-pyridyl)cyclohexane-1,3-diol) and [Co(Hbztpy) 2 ]H[AlW 12 O 40 ]·3H 2 O ( 2 ) (bztpy = 1,2,4,5-tetra(4-pyridyl)benzene), have been hydrothermally synthesized and characterized. Both of them consist of complex supramolecular interactions between inorganic polyanions and organic cations. During the formation process of 1 and 2 , in situ organic reactions involving C-C coupling through dehydrogenative cyclodimerization of two flexible 1,3-bis(4-pyridyl)propane (bpp) molecules were observed. The tetradentate pyridyl chtpy and bztpy molecules serve as 4-connected nodes to enrich the structural topologies of 1 and 2 . The typical centered N-H N (N N = 2.6-2.7 Å) hydrogen bonding interactions link the organic cations to form grid-type networks for capturing the pseudo-spherical Keggin-type anions. The pH values of the reaction solutions are important for the intermolecular C-C coupling of the organic molecules, and their transformation mechanisms are discussed. Grid-type hydrogen bonding networks of organic cations are used to capture pseudo-spherical Keggin-type anionic clusters.