A Unique Asymmetric [Mn] Triple-Stranded Helicate from a Symmetric Pentadentate Ligand

Aromı́, Guillem; Berzal, Paula Carrero; Gámez, Patrick; Roubeau, Olivier; Kooijman, Huub; Spek, Anthony L.; Driessen, Willem L.; Reedijk, Jan

doi:10.1002/1521-3773(20010917)40:18<3444::aid-anie3444>3.0.co;2-q

Cited by 69 publications

(39 citation statements)

References 29 publications

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“…a/Å 9.0509 (10) 9.0287 (7) 33.290 (2) 12.0714 (16) 8.3075 (10) b/Å 11.566 (2) 11.0172 (8) 8.8157 (10) 8.7556 (12) 10.0713 (10) c/Å 11.829 (3) 17.3170 (12) 50.260 (6) 32.284 (6) 35.581 (5) a/° 88.556 (16) 101.844(6)…”

Section: Physical Measurementsunclassified

Complexes of a novel multinucleating poly-β-diketonate ligand

et al. 2004

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Section: Physical Measurementsunclassified

Complexes of a novel multinucleating poly-β-diketonate ligand

et al. 2004

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“…This synthetic procedure provides access to a molecular entity incorporating photoactive spacers separating two 2-hydroxyphenyl/1,3diketonato moieties, each capable of binding two coupled 3d metals. [39] Thus, H4L has been designed for the preparation of molecules featuring two "independent" pairs of metal ions, as seen before, [40] now linked by a photochromic unit. Thus, reactions of H4L under basic conditions with salts of Cu(II), Co(II), Ni(II) or Zn(II), respectively, produce crystals of the corresponding clusters with formulae [M4L2(py)6] (M=Cu, 1; Co, 2; Ni, 3; Zn, 4), exhibiting the predetermined [MM•••MM] topology, as shown by SCXRD for all the compounds.…”

Section: Synthesismentioning

confidence: 99%

Molecules Designed to Contain Two Weakly Coupled Spins with a Photoswitchable Spacer

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García

et al. 2017

Chemistry A European J

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Controlling the charges and spins of molecules lies at the heart of spintronics. A photoswitchable molecule consisting of two independent spins separated by a photoswitchable moiety was designed in the form of new ligand H L, which features a dithienylethene photochromic unit and two lateral coordinating moieties, and yields molecules with [MM⋅⋅⋅MM] topology. Compounds [M L (py) ] (M=Cu, 1; Co, 2; Ni, 3; Zn, 4) were prepared and studied by single-crystal X-ray diffraction (SCXRD). Different metal centers can be selectively distributed among the two chemically distinct sites of the ligand, and this enables the preparation of many double-spin systems. Heterometallic [MM'⋅⋅⋅M'M] analogues with formulas [Cu Ni L (py) ] (5), [Co Ni L (py) ] (6), [Co Cu L (py) ] (7), [Cu Zn L (py) ] (8), and [Ni Zn L (py) ] (9) were prepared and analyzed by SCXRD. Their composition was established unambiguously. All complexes exhibit two weakly interacting [MM'] moieties, some of which embody two-level quantum systems. Compounds 5 and 8 each exhibit a pair of weakly coupled S=1/2 spins that show quantum coherence in pulsed Q-band EPR spectroscopy, as required for quantum computing, with good phase memory times (T =3.59 and 6.03 μs at 7 K). Reversible photoswitching of all the molecules was confirmed in solution. DFT calculations on 5 indicate that the interaction between the two spins of the molecule can be switched on and off on photocyclization.

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“…[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.…”

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

confidence: 99%

“…[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.…”

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

confidence: 99%

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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A Unique Asymmetric [Mn] Triple-Stranded Helicate from a Symmetric Pentadentate Ligand

Cited by 69 publications

References 29 publications

Complexes of a novel multinucleating poly-β-diketonate ligand

Complexes of a novel multinucleating poly-β-diketonate ligand

Molecules Designed to Contain Two Weakly Coupled Spins with a Photoswitchable Spacer

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

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A Unique Asymmetric [Mn] Triple-Stranded Helicate from a Symmetric Pentadentate Ligand

Cited by 69 publications

References 29 publications

Complexes of a novel multinucleating poly-β-diketonate ligand

Complexes of a novel multinucleating poly-β-diketonate ligand

Molecules Designed to Contain Two Weakly Coupled Spins with a Photoswitchable Spacer

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

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