Grafting ligands to direct the self-assembly of Co/Ni2+ substituted polyoxometalate clusters

Ritchie, C., Boyd, T., Long, D. L. , Ditzel, E. and Cronin, L. (2009) Grafting ligands to direct the self-assembly of Co/Ni2+ substituted polyoxometalate clusters. Dalton Transactions(9), pp. 1587-1592. (doi:10.1039/b814076f)

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Abstract

Four transition metal incorporated phosphotungstates have been synthesized through the reaction of Na2WO4, H3PO4, Co/Ni(NO3)(2), and the multifunctional amine N,N'-Bis(2-hydroxyethyl) piperazine (bhep). Na-2{MHbhep(H2O)(4)}[PW10M2O38{Hbhep}(2)] M = Co2+ (1), and Ni2+(2) represent rare examples of complete transition metal chelate encapsulation within a Keggin polyanion. Slight modification of the reaction procedure yielding 1 also yields the two dimensional material (H(2)bhep)(3)Na-4[Co-4(H2O)(2)(PW9O34)(2)].15H(2)O (3). Finally, the isolation of a phosphotungstate cluster containing 18 Co2+ ions is achieved through the bridging of two [Co-9(OH)(3)( H2O)(6)(HPO4)(2)(B-alpha-PW9O34)(3)](16-) clusters by the bhep ligand to form the [{Co-9(OH)(3)( H2O)(3)(HPO4)(2)(B-alpha-PW9O34)(3)}(2) {C8H18N2O2}(3)](32-) dimer (4). The dimerisation process is achieved via the monodentate coordination of the hydroxyl groups from three bhep ligands to each polyanion by displacing the water ligands typically found coordinated to the {Co-9} core forming a nanoscale cylinder-like capsule capped by two {Co9P5W27} with three BHEP-based ligand spacers.

Item Type:Articles
Keywords:CAPSULE CELTIC-RING ISOPOLYOXOTUNGSTATE CLUSTER CLUSTERS COMPLEXES COORDINATION CORE CRYSTAL-STRUCTURES HETEROPOLYANIONS HYBRID IN-SITU ION IONS LIGAND LIGANDS MAGNETIC-PROPERTIES POLYOXOMETALATE POLYOXOMETALATE CLUSTERS POLYOXOTUNGSTATES SELF-ASSEMBLIES self-assembly TRANSITION W-183 NMR WATER
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Long, Dr De Liang and Cronin, Professor Leroy
Authors: Ritchie, C., Boyd, T., Long, D. L., Ditzel, E., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Dalton Transactions
ISSN:1477-9226

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