Self-Assembly of {2}-Metallacryptands and {2}-Metallacryptates

Saalfrank, Rolf W.; Seitz, Verena; Caulder, Dana L.; Raymond, Kenneth N.; Teichert, Markus

doi:10.1002/(sici)1099-0682(199809)1998:9<1313::aid-ejic1313>3.0.co;2-j

Cited by 79 publications

(32 citation statements)

References 52 publications

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“…The presence of transition metals in such systems yields the potential for exhibiting additional functionality, including unusual optical, magnetic, photoactive, catalytic and electrochemical properties. The pyridine containing b-diketones have been known in organic chemistry for a long time [8], but their uses to date in coordination chemistry have been very few [9][10][11][12][13][14]. Recently, metal complexes of functionalized b-diketones ligands have been well reviewed by Tamburini and co-workers [15], some polynuclear complexes and coordination polymers with bis-b-diketones have been reported [16][17][18][19][20][21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

Syntheses, structures and magnetic properties of tetranuclear and trinuclear nickel(II) complexes with β-diketone-functionalized pyridinecarboxylate ligand

Hui

Shu

et al. 2010

Inorganica Chimica Acta

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Section: Introductionmentioning

confidence: 99%

Syntheses, structures and magnetic properties of tetranuclear and trinuclear nickel(II) complexes with β-diketone-functionalized pyridinecarboxylate ligand

Hui

Shu

et al. 2010

Inorganica Chimica Acta

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“…[43][44][45][46][47] Other studies on metal complexes with tri-and tetraketones are quite limited. [48][49][50][51] The present work introduces a new ligand with two separated -diketone functions ( Figure 1). This ligand was expected to be capable of producing both polymeric and discrete complexes ( Figure 2).…”

Section: Introductionmentioning

confidence: 99%

A New Bridging Chelating Ligand for Crystal Engineering: Synthesis, Polymorphism, and Two Modes of Assembly of 1,4-Bis(3-phenyl-1,3-propanedion)benzene with Metal Cations Resulting in Either Discrete or Polymeric Complexes

Soldatov

Zanina

Enright

et al. 2003

Crystal Growth & Design

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This work introduces a new ligand (H 2 L, PhCOCH 2 COPhCOCH 2 COPh) bearing two -diketonate functions separated by a phenylene ring. The free ligand was synthesized and isolated in two polymorphic modifications. The ligand exhibits a preference for one of two basic conformational types where -diketonate functions are approximately coplanar and directed either on opposite sides (trans) or on the same side ∼60°to each other (cis). In the free form, the ligand exists as 100% enol; in the solid state, it adopts a trans conformation. In a onedimensional (1D) coordination polymer [ZnPy 2 L] n *nPy, the ligand adopts the trans conformation and chelates to two zinc(II) centers bridging them at 11.3 Å. In three of the crystals studied, another structure was observed with an ideal formula [M 3 Py 6 L 3 ]*5(CHCl 3 ). In this case, the ligand adopts a cis conformation and chelates to two metal centers bridging them at 10.7 Å, to produce a trinuclear macrocyclic species. In the crystal, these triangles pack to create channels that accommodate chloroform as a guest. The specific crystals studied had the following overall compositions: [Co 3 Py 6 L 3 ]*4.84(CHCl 3 ), [Co 3 Py 6 L 3 ]*4.11(CHCl 3 ), and [Ni 3 Py 6 L 3 ]*4.68(CHCl 3 ). The architecture displays flexibility and zeolite-like behavior.

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“…In contrast, reaction of the bis‐1,3‐diketo dianion (L 2 ) 2− (H 2 L 2 = 2 ) with iron(III) chloride in the presence of alkali‐, alkaline‐earth‐, or rare‐earth‐metal cations (M n + ) yields triple‐stranded {2}‐iron helicates/mesocates {M⊂[Fe 2 (L 2 ) 3 ]}[X] n (M‐ 3 , M=K + , Sr 2+ , Ba 2+ , La 3+ ) 2–4. For example, the metallacryptate Ba‐ 3 is a racemic mixture with either (Δ,Δ)‐ fac ‐ or (Λ,Λ)‐ fac ‐coordinated iron centers (Scheme 1, top right) 2.…”

Section: Methodsmentioning

confidence: 99%

Threading Cesium Ions: Metal, Host, and Ligand Control in Supramolecular Coordination Chemistry

et al. 2006

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Dedicated to Professor Johann Gasteiger on the occasion of his 65th birthdayIn earlier work we demonstrated that the bis-1,3-diketo dianion (L 1 ) 2À is an excellent ligand for the complexation of copper (II) ). [2][3][4] For example, the metallacryptate Ba-3 is a racemic mixture with either[2] However, the two iron centers in meso-[3] The mono-, di-, and trivalent guest cations are endohedrally encapsulated in the cavity of the bicyclic dinuclear host to give [M-3] n+ and their charge is compensated by [FeCl 4 ] À or PF 6 À anions (X À ). Our further studies on the supramolecular coordination chemistry of copper(II) [5] focused on the synthesis of oligonuclear complexes by self-assembly [6] with the 2,6-pyridinylbridged pentadentate ligand (L 2 ) 2À . To this end, we treated 2 [7] with calcium hydride and copper(II) acetate in methanol and isolated the metallacoronate 5 (Scheme 2). We characterized the molecular structure of 5 by X-ray crystallography [8][9][10] of crystals obtained by vapor diffusion of diethyl ether into a solution of 5 in methanol: 5·4 MeOH is present in the crystal as a dinuclear copper(II) coronate, in which a calcium ion is encapsulated in the center, and two acetate ions act as counterions (Figure 1, top). The two crystallographically equivalent copper(II) ions of the idealized-C 2h -symmetric 5[11] have tetragonal-pyramidal coordination geometry, each with two pairs of oxygen donors and one molecule of methanol.In contrast, treatment of a solution of 2 in methanol with copper(II) acetate and cesium carbonate (in place of calcium hydride) does not yield a metallacoronate similar to 5; instead, the larger cesium ion, which prefers a higher coordination number, functions as a template for the formation of the one-dimensional coordination polymer (6) n (Scheme 2). Crystals obtained by vapor diffusion of diethyl Scheme 1. The cation [K-1] + (top left), the dication [Ba-3] 2+ (top right), and the repeating unit in the 1D meso-polymer (4) n (bottom).

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Self-Assembly of {2}-Metallacryptands and {2}-Metallacryptates

Cited by 79 publications

References 52 publications

Syntheses, structures and magnetic properties of tetranuclear and trinuclear nickel(II) complexes with β-diketone-functionalized pyridinecarboxylate ligand

Syntheses, structures and magnetic properties of tetranuclear and trinuclear nickel(II) complexes with β-diketone-functionalized pyridinecarboxylate ligand

A New Bridging Chelating Ligand for Crystal Engineering: Synthesis, Polymorphism, and Two Modes of Assembly of 1,4-Bis(3-phenyl-1,3-propanedion)benzene with Metal Cations Resulting in Either Discrete or Polymeric Complexes

Threading Cesium Ions: Metal, Host, and Ligand Control in Supramolecular Coordination Chemistry

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