Two New<b><i>bis</i></b>-β-Diketones as Ligands for Novel Systems in Supramolecular Chemistry

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

doi:10.1081/scc-120015554

Cited by 19 publications

(13 citation statements)

References 13 publications

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“…[9,10] These functional groups were disposed within ligands with the aim of stimulating the formation of discrete chains of closely spaced transition metals. Such molecular arrangements are interesting on account of their magnetic anisotropy or for their potential application in quantum electronics.…”

Section: Introductionmentioning

confidence: 99%

Designed Topology and Site‐Selective Metal Composition in Tetranuclear [MM′⋅⋅⋅M′M] Linear Complexes

Barrios

Aguilà

Roubeau

et al. 2009

Chemistry A European J

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The ligand 1,3-bis[3-oxo-3-(2-hydroxyphenyl)propionyl]benzene (H(4)L), designed to align transition metals into tetranuclear linear molecules, reacts with M(II) salts (M=Ni, Co, Cu) to yield complexes with the expected [MMMM] topology. The novel complexes [Co(4)L(2)(py)(6)] (2; py=pyridine) and [Na(py)(2)][Cu(4)L(2)(py)(4)](ClO(4)) (3) have been crystallographically characterised. The metal sites in complexes 2 and 3, together with previously characterised [Ni(4)L(2)(py)(6)] (1), favour different coordination geometries. These have been exploited for the deliberate synthesis of the heterometallic complex [Cu(2)Ni(2)L(2)(py)(6)] (4). Complexes 1, 2, 3 and 4 exhibit antiferromagnetic interactions between pairs of metals within each cluster, leading to S=0 spin ground states, except for the latter cluster, which features two quasi-independent S=1/2 moieties within the molecule. Complex 4 gathers the structural and physical conditions, thus allowing it to be considered as prototype of a two-qbit quantum gate.

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Section: Introductionmentioning

confidence: 99%

Designed Topology and Site‐Selective Metal Composition in Tetranuclear [MM′⋅⋅⋅M′M] Linear Complexes

Barrios

Aguilà

Roubeau

et al. 2009

Chemistry A European J

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“…In recent years, some of us have been exploring the coordination chemistry of a phenol-bis(b-diketonate) ligand [12] (H 3 L, see Scheme 1), which was designed for the assembly of rows of closely spaced transition metals. Such an arrangement of 3d metals is of particular interest in the study of magnetic interactions within molecular magnets, and remarkable success has been achieved in this direction with polydentate N-ligands.…”

Section: Introductionmentioning

confidence: 99%

Aggregation of [Cu${{\bf }{{{\bf II}\hfill \atop \bf 4\hfill}}}$] Building Blocks into [Cu${{\bf }{{{\bf II}\hfill \atop \bf 8\hfill}}}$] Clusters or a [Cu${{\bf }{{{\bf II}\hfill \atop \bf 4\hfill}}}$]_∞ Chain through Subtle Chemical Control

Aromı́

Ribas

Gámez

et al. 2004

Chemistry A European J

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Coordination complexes of the ligand H3L [1,3-bis(3-oxo-3-phenylpropionyl)-2-hydroxy-5-methylbenzene] with Cu(II) are reported. Clusters showing various nuclearities or modes of supramolecular organization have been prepared by slightly changing the reaction conditions and have been crystallographically characterized. The reaction of H3L with one equivalent of Cu(OAc)2 in DMF yields the dinuclear complex [Cu2(HL)2(dmf)2] (1). Reaction in MeOH of H3L with an increased amount of metal, in the form of Cu(NO3)2, and excess strong base (nBu4NOH) affords the cluster [Cu8(L)2(OMe)8(NO3)2] (2). Complex 2 is a dimer of two linear [Cu4] arrays bridged by methoxide ligands, where the polynucleating ligand is fully deprotonated. The [Cu4]2 clusters are linked to each other by NO3- bridges to form one-dimensional coordination polymers. The link between [Cu8] units and their relative spatial positioning can be modified by changing the anion of the Cu(II) salt, as demonstrated by the synthesis of the cluster polymers [Cu8(L)2(OMe)8Cl2] (3) and [Cu8(L)(OMe)7.86Br2.14] (4), where only NO3- has been replaced by Cl- or Br-, respectively. Similarly, when ClO4- is used, compound [Cu8(L)2(OMe)8(ClO4)2(MeOH)4] (5) can be isolated. It contains independent [Cu8] units. A slight change in the stoichiometry of the reaction leading to 2 affords the related complex catena-[Cu4(L)(OMe)3(NO3)2(H2O)0.36] (6). This polymer contains essentially the same [Cu4] moiety as 2, albeit organized in a completely different arrangement. Each [Cu4] unit in 6 is linked by OMe- ligands to two such equivalent groups to form an infinite chain. Magnetic susceptibility measurements reveal weak antiferromagnetic exchange between Cu(II) centers in 1 (J = -0.73 cm(-1)) and strong antiferromagnetic coupling within [Cu4] chains in 2, 5, and 6 (most negative J values of -113.8 and -177.3 cm(-1) for 2 and 6, respectively).

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“…[ Scheme 1), [15,16] aimed at forming molecular strings of metal ions in close proximity. Maximum occupancy of their coordination pockets would result in tetranuclear clusters in form of [M 4 ] chains [17] for H 3 L1 and aligned [M 2 ] 2 dimers of dimers for H 4 L2.…”

Section: Abstract: Ligand Design / O Ligands / Nmr Spectroscopy / Magmentioning

confidence: 99%

“…Of these molecular species, only a minority have the metal ions disposed in close proximity so as to show cooperative effects resulting from strong magnetic-exchange interactions [13] or metalmetal bonding. [14] We have been interested in preparing new ligands incorporating various β-diketone units and other donor groups in a linear fashion (H 3 L1 and H 4 L2 in [ Scheme 1), [15,16] aimed at forming molecular strings of metal ions in close proximity. Maximum occupancy of their coordination pockets would result in tetranuclear clusters in form of [M 4 ] chains [17] for H 3 L1 and aligned [M 2 ] 2 dimers of dimers for H 4 L2.…”

Section: (Py) 5 ] (1) Which Displays An Un-mentioning

confidence: 99%

“…This second course of action has led to the production of a large amount of polynuclear edifices displaying sophisticated shapes and architectures, such as helicates, [9] grids, [10] cylinders, [11] catenates, [12] and many more. Of these molecular species, only a minority have the metal ions disposed in close proximity so as to show cooperative effects resulting from strong magnetic-exchange interactions [13] or metalmetal bonding.[ Scheme 1), [15,16] aimed at forming molecular strings of metal ions in close proximity. Maximum occupancy of their coordination pockets would result in tetranuclear clusters in form of [M 4 ] chains [17] for H 3 L1 and aligned [M 2 ] 2 dimers of dimers for H 4 L2.…”

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A Zig‐Zag [Mn^II₄] Cluster from a Novel Bis(β‐diketonate) Ligand

et al. 2006

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Keywords: Ligand design / O ligands / NMR spectroscopy / Magnetism / MnA new ligand, H 5 L3, has been synthesized featuring seven linearly arranged oxygen donors in form of two 1,3-diketone and three phenol groups. The X-ray structure of H 5 L3 unveils a rare case where one of the diketones is in the enolic form and the other one in the bis(carbonyl) form. This structure is shown by 1 H NMR to persist in solution. Reaction of H 5 L3 with Mn(AcO) 2 in pyridine leads to the novel tetranuclear cluster [Mn 4 (H 2 L3) 2 (OAc) 2 (py) 5 ] (1), which displays an un-The preparation of molecular cluster complexes of interacting transition-metal ions is useful to areas as important and diverse as molecular magnetism, [1,2] homogeneous catalysis [3] or bioinorganic chemistry. [4,5] A very successful approach for accessing such species has been the assembly of metal ions by means of small bridging ligands, such as carboxylates, where growth into infinite arrays is often prevented by additional terminal ligands. [6,7] Such a method has been sometimes termed "serendipitous approach" since it does not allow prediction of the structure of the final species.[8] An alternative strategy has been the design and preparation of complicated multidentate ligands favoring the assembly of metal ions into aggregates with topologies that may be anticipated from the structure of these ligands. This second course of action has led to the production of a large amount of polynuclear edifices displaying sophisticated shapes and architectures, such as helicates, [9] grids, [10] cylinders, [11] catenates, [12] and many more. Of these molecular species, only a minority have the metal ions disposed in close proximity so as to show cooperative effects resulting from strong magnetic-exchange interactions [13] or metalmetal bonding.[ Scheme 1), [15,16] aimed at forming molecular strings of metal ions in close proximity. Maximum occupancy of their coordination pockets would result in tetranuclear clusters in form of [M 4 ] chains [17] for H 3 L1 and aligned [M 2 ] 2 dimers of dimers for H 4 L2. Reactions of the latter with M(OAc) 2 salts have resulted invariably in the formation of complexes of the type [M 2 (H 2 L2) 2 (S) n ] (n = 2 or 4; S = solvent; M = Mn, Ni, Co, Cu).[16] Similar dinuclear compounds have been obtained with H 3 L1.[18] However, in the absence of a coordinating solvent, molecules exhibiting higher occupancy, [Co 3 (HL1) 3 ] and [Mn 3 (HL1) 3 ], were characterized, which represented a new asymmetric topology within the context of coordination helicates. [19] Inspired by these early results, we have now designed and synthesized a new ligand displaying as many as six adjacent coordination pockets (H 5 L3, Scheme 1). Reaction of H 5 L3 with Mn II produces a very rare magnetically exchanged tetranuclear complex featuring an [Mn 4 O 6 ] core in form of a zig-zag chain.The new ligand H 5 L3 {2-hydroxy-1,3-bis[3-(2-hydroxyphenyl)-3-oxopropionyl]benzene} was prepared from the methoxide derivative H 4 L4 (Scheme 1).[20] The latter is also a n...

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Two Newbis-β-Diketones as Ligands for Novel Systems in Supramolecular Chemistry

Cited by 19 publications

References 13 publications

Designed Topology and Site‐Selective Metal Composition in Tetranuclear [MM′⋅⋅⋅M′M] Linear Complexes

Designed Topology and Site‐Selective Metal Composition in Tetranuclear [MM′⋅⋅⋅M′M] Linear Complexes

Aggregation of [Cu${{\bf }{{{\bf II}\hfill \atop \bf 4\hfill}}}$] Building Blocks into [Cu${{\bf }{{{\bf II}\hfill \atop \bf 8\hfill}}}$] Clusters or a [Cu${{\bf }{{{\bf II}\hfill \atop \bf 4\hfill}}}$]_∞ Chain through Subtle Chemical Control

A Zig‐Zag [Mn^II₄] Cluster from a Novel Bis(β‐diketonate) Ligand

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Two Newbis-β-Diketones as Ligands for Novel Systems in Supramolecular Chemistry

Cited by 19 publications

References 13 publications

Designed Topology and Site‐Selective Metal Composition in Tetranuclear [MM′⋅⋅⋅M′M] Linear Complexes

Designed Topology and Site‐Selective Metal Composition in Tetranuclear [MM′⋅⋅⋅M′M] Linear Complexes

Aggregation of [Cu${{\bf }{{{\bf II}\hfill \atop \bf 4\hfill}}}$] Building Blocks into [Cu${{\bf }{{{\bf II}\hfill \atop \bf 8\hfill}}}$] Clusters or a [Cu${{\bf }{{{\bf II}\hfill \atop \bf 4\hfill}}}$]∞ Chain through Subtle Chemical Control

A Zig‐Zag [MnII4] Cluster from a Novel Bis(β‐diketonate) Ligand

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Aggregation of [Cu${{\bf }{{{\bf II}\hfill \atop \bf 4\hfill}}}$] Building Blocks into [Cu${{\bf }{{{\bf II}\hfill \atop \bf 8\hfill}}}$] Clusters or a [Cu${{\bf }{{{\bf II}\hfill \atop \bf 4\hfill}}}$]_∞ Chain through Subtle Chemical Control

A Zig‐Zag [Mn^II₄] Cluster from a Novel Bis(β‐diketonate) Ligand