Structural and metallo selectivity in the assembly of [2 x 2] grid-type metallosupramolecular species: Mechanisms and kinetic control

A.R. Stefankiewicz, J. Harrowfield, A. Madalan, K. Rissanen, Alexandre Sobolev, J.M. Lehn

Research output: Contribution to journalReview article

32 Citations (Scopus)

Abstract

An unsymmetrical bis(tridentate) ligand LH in which one binding site can be readily deprotonated forms a kinetically inert [Co(III)L-2](+) complex which can be used as a "corner" species for the "Coupe du Roi" assembly of trans, trans-[Co2M2L4](6+) metallogrids (M = Fe(II), Co(II), Cu(II), Zn(II)). In the mixed Co(III)/Co(II) species, the oxidation states appear to be localised. In solution, the ligand LH forms octacationic, homometallic [2 x 2] grids with the individual labile metal ions Fe(II), Co(II), Cu(II), Zn(II), seemingly as mixtures of all possible isomers arising from the unsymmetrical nature of the ligand. In the solid state, however, [Zn4L4](CF3SO3)(8)center dot 4CH(3)CN crystallises as a single species where the cation has S-4 symmetry. This stereoselectivity in the crystalline lattice is associated with interactions between the cation and triflate anions which can again be analysed in terms of the Coupe du Roi concept.
Original languageEnglish
Pages (from-to)12320-12332
JournalJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
Volume40
Issue number45
DOIs
Publication statusPublished - 2011

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