Hybrid Host-Guest Complexes: Directing the Supramolecular Structure through Secondary Host-Guest Interactions

Streb, C., McGlone, T., Brucher, O., Long, D. L. and Cronin, L. (2008) Hybrid Host-Guest Complexes: Directing the Supramolecular Structure through Secondary Host-Guest Interactions. Chemistry: A European Journal, 14(29), pp. 8861-8868. (doi:10.1002/chem.200801247)

Full text not currently available from Enlighten.

Abstract

A set of four hybrid hostguest complexes based on the inorganic crown ether analogue [H12W36O120](12)({W-36}) have been isolated and characterised. The cluster anion features a central rigid binding site made up of six terminal oxygen ligands and this motif allows the selective binding of a range of alkali and alkali-earth-metal cations. Here, the binding site was utilised to functionalise the metal oxide-based cavity by complexing a range of protonated primary amines within the recognition site. As a result, a set of four hybrid organic-inorganic hostguest complexes were obtained whereby the interactions are highly directed specifically within this cavity. The guest cations in these molecular assemblies range from the aromatic 2-phenethylamine (1) and 4-plienylbutylamine (2) to the bifunctional aromatic p-xylylene diamine (3) and the aliphatic, bifunctional 1,6-diaminohexane (4). Compounds 1-4 were structurally characterised by single-crystal X-ray diffraction, elemental analysis, flame atomic absorption spectroscopy, FTIR and bond valence sum calculations. This comparative study focuses on the supramolecular effects of the amine guest cations and investigates their structure-directing effects on the framework arrangement arising by locking the protonated amines within the cavity of the {W-36} cluster. It was shown that parts of the organic guest cation protrude from the central binding cavity and the nature of this protruding organic "tail" directs the solid-state arrangement of compounds 1-4. Guest cations with a hydrophobic phenyl tail result in an anti-parallel assembly of {W-36} complexes arranged in a series of pillared layers. As a consequence, no direct supramolecular interactions between {W-36} clusters are observed. In contrast, bifunctional guest cations with a secondary amino binding site act as molecular connectors and directly link two Cluster units thus locking the supramolecular assembly in a tilted arrangement. This direct linking Of (W-36} anions results in the formation of an infinite supramolecular scaffold.

Item Type:Articles
Keywords:ABSORPTION ANION ANIONS ASSEMBLIES BINDING BOND BUILDING-BLOCKS CATION CATIONS CELTIC-RING ISOPOLYOXOTUNGSTATE CLUSTER CLUSTERS COMPLEX COMPLEXES crown compounds CROWN-ETHER DIFFRACTION ELECTRON-TRANSFER REACTIONS FEATURES FTIR GROWTH HOST-GUEST INTERACTIONS host-guest systems HYBRID hybrid materials LIGAND LIGANDS NANOSTRUCTURES POLYOXOMETALATE CHEMISTRY RECOGNITION self-assembly SOLID-STATE SPECTROSCOPY Structure Supramolecular Chemistry SYMMETRY SYNTHONS UNIT UNITS VALENCE X-RAY X-ray diffraction X-RAY-DIFFRACTION
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Long, Dr Deliang and Cronin, Professor Lee and Streb, Mr Carsten
Authors: Streb, C., McGlone, T., Brucher, O., Long, D. L., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry: A European Journal
ISSN:0947-6539
ISSN (Online):1521-3765

University Staff: Request a correction | Enlighten Editors: Update this record