Two New bis‐β‐Diketones as Ligands for Novel Systems in Supramolecular Chemistry.

Aromı́, Guillem; Gámez, Patrick; Berzal, Paula Carrero; Driessen, Willem L.; Reedijk, J.

doi:10.1002/chin.200322038

Cited by 3 publications

(6 citation statements)

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“…[12][13][14] We recently reported the synthesis of the pentadentate ligand 1,3-bis-(3-oxo-3-phenylpropionyl)-2-hydroxy-5-methylbenzene (H 3 L, see scheme I). 11 The structure of this molecule displays two b-diketone units and one phenol group, disposing five oxygen donor atoms in a linear array, aimed at inducing the aggregation of transition metals in the form of short, molecular chains. The coordination chemistry of this compound has proven very varied, leading to an extensive series of dinuclear, 15 trinuclear, 16,17 octanuclear 18 or one-dimensional infinite species.…”

Section: Introductionmentioning

confidence: 99%

“…Some structural motifs recreated in this manner are squares, 9 grids 5 or linear chains 10 of closely spaced paramagnetic centers. We have been engaged for some time 11 in the synthesis of new polynucleating ligands possessing oxygen as donating atoms, primarily as poly-b-diketone moieties, aimed at obtaining novel structural motifs in cluster coordination chemistry. A few complexes of poly-b-diketone ligands have been published previously by other groups.…”

Section: Introductionmentioning

confidence: 99%

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Complexes of a novel multinucleating poly-β-diketonate ligand

et al. 2004

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Complexes of a novel multinucleating poly-β-diketonate ligand

et al. 2004

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“…[3] Initial efforts into the investigation of its coordination properties involved reactions with Mn II ions, and led to the preparation of a trinuclear complex with formula [Mn 3 (HL) 3 ] which displayed an asymmetric array of metals. [1] This approach is starting to take hold in the area of molecular magnetism.…”

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confidence: 99%

“…[1] This approach is starting to take hold in the area of molecular magnetism. [3] Initial efforts into the investigation of its coordination properties involved reactions with Mn II ions, and led to the preparation of a trinuclear complex with formula [Mn 3 (HL) 3 ] which displayed an asymmetric array of metals. [2] We have reported the synthesis of an O-pentadentate donor possessing a phenol and two b-diketone units (H 3 L), which was conceived to direct the formation of chains of closely spaced transition metals.…”

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Ligand-Templated Four-Metal Chains Dimerize into a Unique [CuII8] Cluster

et al. 2002

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Within the context of what has been termed coordination supramolecular chemistry, remarkable progress has been made in the design and preparation of multidentate ligands capable of participating in complicated molecular structures upon complexation, in predetermined manners, with transition metals. [1] This approach is starting to take hold in the area of molecular magnetism. Thus, in recent years, a few important reports have appeared describing the formation of new magnetic transition metal clusters through the template action of specifically designed multinucleating ligands. [2] We have reported the synthesis of an O-pentaden-tate donor possessing a phenol and two b-diketone units (H 3 L), which was conceived to direct the formation of chains of closely spaced transition metals. [3] Initial efforts into the investigation of its coordination properties involved reactions with Mn II ions, and led to the preparation of a trinuclear complex with formula [Mn 3 (HL) 3 ] which displayed an asym-metric array of metals. [4] A significant step forward in the exploration of the templating capability of this new ligand is reported here with the fascinating methoxide-mediated aggregation of two ligand-templated [Cu 4 ] chains into an entirely new octanuclear Cu II cluster held together by a fully deprotonated form of H 3 L. The title compound was prepared by treating a methanolic solution of Cu(NO 3) 2 ¥ 3 H 2 O with a solution containing 0.125 equivalents of H 3 L and 1.8 equivalents of NtBu 4 OH in MeOH. The green powder that precipitated was recrystallized from MeOH/Et 2 O to yield green crystals of [{Cu 4 (L)(OMe) 4-(NO 3)} 2 ] (1) [5] in an overall yield of 21 %. The organic salt is introduced into the reaction mixture as the base necessary to deprotonate H 3 L and also as the acceptor of the protons from methanol to give the MeO À ions that become incorporated into the complex. The fact that the complex binds methoxide instead of hydroxide ions despite the larger Br˘nsted basicity of the former can be explained by the stability of the final product combined with the large excess of methanol present in the system. The latter point is supported by the observation that, upon prolonged exposure to air, complex 1 changes color from green to brown, presumably following a process of complete hydrolysis of the methoxide ligands, as suggested by elemental analysis. [6] The structure of 1 [7] (Figure 1) shows a unique [Cu II 8 ] cluster formed by the dimerization of two ligand-held four-metal atom rows. Both metallic chains are bound to each other through eight methoxide ligands: six in a triply bridging Figure 1. POV-Ray representation of [{Cu 4 (L)(OMe) 4 (NO 3)} 2 ] (1), where the axial bonds around the Cu II ions are highlighted by striped lines. manner [8] and two in a m-OMe À fashion. The coordination around the Cu centers is completed by nitrate ions, which connect, in an extremely unusual h 3 :m 3-NO 3 À mode, [9] the [Cu 8 ] units into one-dimensional polymeric chains of clusters parallel to the a-axis (Figure 2). In...

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“…In this context, we have built in the same molecule two b-diketone units and a phenol group to produce a symmetric O-pentadentate ligand (H 3 L). [3] The preparation of some related molecules and their use as dinucleating ligands have been reported in the literature. [4] We intended to use a basic form of H 3 L as a template to bring in proximity a number of transition metals in discrete, molecular arrays.…”

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confidence: 99%