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• W216797788 abstract "This is an electronic version of an article published in J. Coord. Chem. 2010, 63, 2779 – 2789.The Journal of Coordination Chemistry is available online at: http://pdfserve.informaworld.com/702484_915549761_923032400.pdf A Ferrocene-Based Catecholamide Ligand: the Consequences of Ligand Swivel for Directed Supramolecular Self-Assembly Jeffrey S. Mugridge, Dorothea Fiedler, Kenneth N. Raymond* Department of Chemistry, University of California, Berkeley, Berkeley CA 94720, and Lawrence Berkeley National Laboratory, Chemical Sciences Division, Berkeley, CA 94720 * Corresponding author. Email: raymond@socrates.berkeley.edu A ferrocene-based biscatecholamide ligand was prepared and investigated for formation of metal-ligand supramolecular assemblies with different metals. Reaction with Ge(IV) was found to result in formation of a variety of Ge n L m coordination complexes, including [Ge 2 L 3 ] 4- and [Ge 2 L 2 (μ-OMe) 2 ] 2- . The ligand’s ability to swivel about the ferrocenyl linker and adopt different conformations accounts for the formation of many different Ge n L m species. This study demonstrates why conformational ligand rigidity is essential in the rational design and directed self-assembly of supramolecular complexes. Keywords: Self-assembly; Supramolecular; Ferrocene; Conformational flexibility; Ligand design 1. Introduction Recent interest in the fields of supramolecular chemistry, self-assembly and host-guest recognition has produced a large diversity of synthetic supramolecular assemblies. One common approach to the design and synthesis of such assemblies is the use of labile, metal-ligand interactions. Appropriately chosen ligand symmetries and incommensurate coordination numbers between ligand and metal can be used to direct the reversible self-assembly of complex supramolecular architectures [1-5]. This strategy has allowed the preparation of many metal- ligand based supramolecular structures such as rotaxanes and catenanes [6-8], helicates [9-11] and molecular squares, rings, grids and polyhedra [12-18]. We have previously reported on the design, synthesis and structural dynamics of triple- stranded metallohelicates [11, 19-20] and tetrahedral host assemblies [4, 15, 21-25], each constructed from ligand scaffolds that use catecholamide chelating units and rely on ligand planarity for unique formation (Figure 1). In this article we examine the coordination chemistry of a ferrocene-based biscatecholamide ligand (L, Figure 2). While the extended conformation of L is similar in shape and symmetry to the naphthalene-based ligand (Figure 1, left), which readily self-assembles into a molecular tetrahedron, the ferrocene linker in L introduces one additional internal rotational freedom, a swivel, that allows formation of a variety of M-L coordination complexes. Figure 1. Schematic structures of previously prepared metallohelicate (left) and tetrahedral (right) supramolecular assemblies, only one ligand on each is shown for clarity. Note that each" @default.
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• W216797788 date "2011-06-01" @default.
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• W216797788 title "A Ferrocene-Based Catecholamide Ligand: the Consequences of Ligand Swivel for Directed Supramolecular Self-Assembly" @default.
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