Abstract
The two [3.3.1] metallacryptate complexes, namely, poly[[μ3-acetato-hexa-kis-(μ-N,N-di-methyl-formamide)-bis-(N,N-di-methyl-formamide)bis-[salicyl-hydroxi-mato(2-)]hepta-kis-[salicyl-hydrox-im-ato(3-)]hexa-aluminium(III)dysprosium(III)penta-sodium(I)] N,N-di-methyl-formamide tetra-solvate monohydrate], [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8]·4DMF·H2O or {[DyAl6Na5(C7H5NO3)2(C7H4NO3)7(C2H3O2)(C3H7NO)8]·4C3H7NO·H2O} n , 1, and poly[[di-μ4-acetato-nona-kis-(μ-N,N-di-methyl-form-amide)-octa-kis-(N,N-di-methyl-formamide)tetra-kis-[sali-cyl-hydroximato(2-)]tetra-deca-kis-[salicyl-hydroximato(3-)]dodeca-aluminium(III)didysprosium(III)deca-sodium(I)] N,N-di-methyl-form-amide 6.335-solvate], [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8.5]2·6.335DMF or {[Dy2Al12Na10(C7H5NO3)4(C7H4NO3)14(C2H3O2)2(C3H7NO)17]·6.335C3H7NO} n , 2, where shi3- is salicyl-hydroximate and DMF is N,N-di-methyl-formamide, both consist of an aluminium-based metallacryptand. In 1 and 2, the metallacryptand encapsulates a dysprosium(III) ion in the central cavity, and the resulting metallacryptates are connected to each other via sodium-DMF linkages to generate a two-dimensional sheet. The metallacryptates of 1 and 2 are the three-dimensional analogues of metallacrowns as the metallacryptates contain a metal-nitro-gen-oxygen cyclic repeat unit throughout the complexes. For 1 the building block of the two-dimensional sheet is comprised of only one type of metallacryptate, which is connected to four neighboring metallacryptates via four sodium-DMF linkages. In 2, the building block is a dimeric unit of two metallacryptates. Each dimeric metallacryptate unit is connected to four other dimeric units via six sodium-DMF linkages. The two metallacryptates of each dimeric unit can be considered enanti-omers of each other. In both 1 and 2, chirality is imparted to the metallacryptate due to the Λ and Δ propeller configurations of the four octa-hedral aluminium ions of the metallacryptand shell.
Highlights
The two [3.3.1] metallacryptate complexes, namely, poly[[3-acetato-hexakis(N,N-dimethylformamide)bis(N,N-dimethylformamide)bis[salicylhydroximato(2À)]heptakis[salicylhydroximato(3À)]hexaaluminium(III)dysprosium(III)pentasodium(I)] N,N-dimethylformamide tetrasolvate monohydrate], [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8]Á4DMFÁH2O or {[DyAl6Na5(C7H5NO3)2(C7H4NO3)7(C2H3O2)(C3H7NO)8]Á4C3H7NOÁH2O}n, 1, and poly[[di-4-acetato-nonakis(-N,N-dimethylformamide)octakis(N,N-dimethylformamide)tetrakis[salicylhydroximato(2-)]tetradecakis[salicylhydroximato(3À)]dodecaaluminium(III)didysprosium(III)decasodium(I)] N,N-dimethylformamide 6.335-solvate], [DyAl6Na5(OAc)(Hshi)2(shi)7(DMF)8.5]2Á6.335DMF or {[Dy2Al12Na10(C7H5NO3)4(C7H4NO3)14(C2H3O2)2(C3H7NO)17]Á6.335C3H7NO}n, 2, where shi3À is salicylhydroximate and DMF is N,N-dimethylformamide, both consist of an aluminium-based metallacryptand
For 1 the building block of the two-dimensional sheet is comprised of only one type of metallacryptate, which is connected to four neighboring metallacryptates via four sodium–DMF linkages
The archetypal metallacrown (MC) framework is based on a cyclic metal–nitrogen–oxygen repeat unit similar to the crown ether cyclic carbon–carbon–oxygen repeat unit
Summary
Metallacrowns, first recognized in 1989 by Pecoraro (Pecoraro, 1989), belong to a class of molecules known as metallamacrocycles that include, but are not limited to, metallahelices and metallahelicates (Kramer et al, 1993; Piguet et al, 1997), metallacryptands and metallacryptates (Ma et al, 1980; Saalfrank et al, 1988; Zaleski et al, 2005), and metallic wheels and rings (Taft et al, 1994; Muller et al, 1995; Murrie et al, 1999). The archetypal metallacrown (MC) framework is based on a cyclic metal–nitrogen–oxygen repeat unit similar to the crown ether cyclic carbon–carbon–oxygen repeat unit. Metallacrown and metallacryptate chemistry has mainly focused on incorporating transition metal ions in the ring repeating unit as these ions impart interesting magnetic and spectroscopic properties. One hallmark of MC chemistry is the ability to substitute components of the complexes and still generate similar structures. Complexes 1 and 2 represent the first metallacrowns or metallacryptates to contain aluminum as a ring metal. For many metallacrowns and metallacryptates, a common ligand is salicylhydroxamic acid (H3shi), which can be triply deprotonated to produce salicylhydroximate (shi3À), and when this ligand set is combined with transition-metal ions in a
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