title: Self-assembly of hybrid organic-inorganic polyoxovanadates: functionalised mixed-valent clusters and molecular cages.
abstract: Herein we report the intra- and inter-molecular assembly of a {V(5)O(9)} subunit. This mixed-valent structural motif can be stabilised as [V(5)O(9)(L(1-3))(4)](5-/9-) (1-3) by a range of organoarsonate ligands (L(1)-L(3)) whose secondary functionalities influence its packing arrangement within the crystal structures. Variation of the reaction conditions results in the dodecanuclear cage structure [V(12)O(14)(OH)(4)(L(1))(10)](4-) (4) where two modified convex building units are linked via two dimeric {O(4)V(IV)(OH)(2)V(IV)O(4)} moieties. Bi-functional phosphonate ligands, L(4)-L(6) allow the intramolecular connectivity of the {V(5)O(9)} subunit to give hybrid capsules [V(10)O(18)(L(4-6))(4)](10-) (5-7). The dimensions of the electrophilic cavities of the capsular entities are determined by the incorporated ligand type. Mass spectrometry experiments confirm the stability of the complexes in solution. We investigate and model the temperature-dependent magnetic properties of representative complexes 1, 4, 6 and 7 and provide preliminary cell-viability studies of three different cancer cell lines with respect to Na(8)H(2)[6]·36H(2)O and Na(8)H(2)[7]·2DMF·29H(2)O.
authors.affiliation: School of Chemistry & CRANN, University of Dublin, Trinity College, Dublin 2, Ireland.
authors.forename: John M
authors.initials: JM
authors.lastname: Breen
authors.forename: Rodolphe
authors.initials: R
authors.lastname: Clérac
authors.forename: Lei
authors.initials: L
authors.lastname: Zhang
authors.forename: Suzanne M
authors.initials: SM
authors.lastname: Cloonan
authors.forename: Elaine
authors.initials: E
authors.lastname: Kennedy
authors.forename: Martin
authors.initials: M
authors.lastname: Feeney
authors.forename: Thomas
authors.initials: T
authors.lastname: McCabe
authors.forename: D Clive
authors.initials: DC
authors.lastname: Williams
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Schmitt
mesh_terms: D008024:Ligands; D060328:Magnetic Phenomena; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D014638:Vanadates / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D011108:Polymers; D014638:Vanadates