Slow Magnetization Relaxation in Unprecedented MnIII4DyIII3 and MnIII4DyIII5 Clusters from the Use of N-Salicylidene-o-aminophenol

Alexandropoulos, Dimitris I.; Nguyen, Tu N.; Cunha-Silva, Luı́s; Zafiropoulos, Theodoros F.; Escuer, Albert; Christou, George; Stamatatos, Theocharis C.

doi:10.1021/ic302505p

Cited by 43 publications

(19 citation statements)

References 24 publications

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“…Our group has had a longstanding interest in the use of Schiff base ligands that resemble the scaffold of the well-known N-salicylidene-o-aminophenol (saphH 2 , Scheme 1) chelate towards the synthesis of nanosized 3d-and 4f-metal compounds with potentially interesting magnetic and optical properties [16,17]. The first member of this family of chelates has been the N-salicylidene-2-amino-5-chlorobenzoic acid (sacbH 2 , Scheme 1), a tetradentate chelating and bridging ligand that has proved its ability to stabilize high-nuclearity 3d-metal clusters [18] and polymers [19] with unprecedented structures but with rather trivial magnetic properties.…”

Section: Introductionmentioning

confidence: 99%

4f-Metal Clusters Exhibiting Slow Relaxation of Magnetization: A {Dy7} Complex with An Hourglass-like Metal Topology

et al. 2020

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The reaction between Dy(NO3)3∙6H2O and the bulky Schiff base ligand, N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in the presence of the organic base NEt3 has led to crystallization and structural, spectroscopic and magnetic characterization of a new heptanuclear [Dy7(OH)6(OMe)2(NO3)1.5(nacb)2(nacbH)6(MeOH)(H2O)2](NO3)1.5 (1) compound in ~40% yield. Complex 1 has a unique hourglass-like metal topology, among all previously reported {Dy7} clusters, comprising two distorted {Dy4(μ3-OH)3(μ3-OMe)}8+ cubanes that share a common metal vertex (Dy2). Peripheral ligation about the metal core is provided by the carboxylate groups of four η1:η1:η1:μ single-deprotonated nacbH− and two η1:η1:η2:η1:μ3 fully-deprotonated nacb2− ligands. Complex 1 is the first structurally characterized 4f-metal complex bearing the chelating/bridging ligand nacbH2 at any protonation level. Magnetic susceptibility studies revealed that 1 exhibits slow relaxation of magnetization at a zero external dc field, albeit with a small energy barrier of ~5 K for the magnetization reversal, most likely due to the very fast quantum-tunneling process. The combined results are a promising start to further explore the reactivity of nacbH2 upon all lanthanide ions and the systematic use of this chelate ligand as a route to new 4f-metal cluster compounds with beautiful structures and interesting magnetic dynamics.

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Section: Introductionmentioning

confidence: 99%

4f-Metal Clusters Exhibiting Slow Relaxation of Magnetization: A {Dy7} Complex with An Hourglass-like Metal Topology

et al. 2020

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“…Considering the significant effect of the organic chelate ligand on the synthesis of new coordination compounds with interesting structural and magnetic properties, our group has started a program aiming at the exploration of the coordination affinity of various Schiff base ligands, related to the parent N-salicylidene-o-aminophenol (saphH 2 , Scheme 1), with magnetically interesting 3d-and 4f-metal ions, and 3d/4f-metal combinations [19]. The ligand of choice for this work was N-salicylidene-2-amino-5-chlorobenzoic acid (sacbH 2 , Scheme 1), which-upon complete deprotonation-can act as a tetradentate (O 3 N) chelating and bridging ligand to both di-and trivalent metal ions, thus yielding structurally interesting polynuclear metal complexes.…”

Section: Introductionmentioning

confidence: 99%

‘Metal Complexes as Ligands’ for the Synthesis of Coordination Polymers: A MnIII Monomer as a Building Block for the Preparation of an Unprecedented 1-D {MnIIMnIII}n Linear Chain

et al. 2020

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A relatively unexplored synthetic route in redox-active Mn(II/III) coordination chemistry has been employed toward the preparation of a new mixed-valence MnII/III 1-D linear chain from the reaction of [MnIII(sacb)2]− precursor with a MnII source, where sacbH2 is the Schiff base ligand N-salicylidene-2-amino-5-chlorobenzoic acid. The mononuclear (Pr2NH2)[MnIII(sacb)2] (1) compound was obtained in excellent yields (>85%) from the 1:2:3 reaction of Mn(O2CMe)2∙4H2O, sacbH2 and Pr2NH, respectively. In 1, the two doubly deprotonated sacb2− ligands act as Ocarboxylate,Nimine,Ophenoxide-tridentate chelates, while the second carboxylate O atom of sacb2− is dangling and H-bonded to the Pr2NH2+ countercation. Complex 1 was subsequently used as a ‘ligand’ to react stoichiometrically with the ‘metal’ Mn(NO3)2∙4H2O, thus leading to the 1-D coordination polymer {[MnIIMnIII(sacb)2(H2O)2(MeOH)2](NO3)}n (2) in good yields (~50%). The removal of Pr2NH2+ from the vicinity of the [MnIII(sacb)2]− metalloligand has rendered possible (vide infra) the coordination of the second Ocarboxylate of sacb2− to neighboring {MnII(H2O)2(MeOH)2}2+ units, and consequently the formation of the 1-D polymer 2. Direct-current (dc) magnetic susceptibility studies revealed the presence of very weak antiferromagnetic exchange interactions between alternating MnIII and MnII atoms with a coupling constant of J = −0.08 cm−1 for g = 2.00. The combined results demonstrate the potential of the ‘metal complexes as ligands’ approach to yield new mixed-valence Mn(II/III) coordination polymers with interesting structural motifs and physicochemical properties.

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“…[27][28][29] We have begun to focus efforts on investigating the synthesis and properties of soluble coordination polymers and the potential to use them as a base to synthesise new materials. We selected the simple Schiff base salicylidene-2-aminophenol (H2L) on the basis that it has previously produced SMMs, [30][31][32] clusters [33][34][35] and coordination polymers. 36 This ligand can also form discrete species with ancillary ligands 37 and replacement of the latter with bridging ligands may potentially lead to coordination polymers.…”

Section: Introductionmentioning

confidence: 99%

A Bridge Too Far: Testing the Limits of Polypyridyl Ligands in Bridging Soluble Subunits of a Coordination Polymer

Beddoe

Fitzpatrick

Price

et al. 2017

Crystal Growth & Design

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Starting with a coordination polymer, {[Cu(L)]2}n (1 where H2L = salicylidene-2-aminophenol), we have explored the ability of polypyridyl ligands (P) to bridge the monomer complex to form nine {[Cu(L)]2(P)} complexes. The identity and solution stability of the [Cu(L)] units has been investigated through a novel combined UV-vis/EPR experiment and it has been found to be a stable supramolecular building unit for the construction of discrete complexes and coordination polymers. The reorganisation of [Cu(L)] units to a new coordination polymer on addition of 4,4'-bipyridine markedly changes the connectivity of the structure and the magnitude of the antiferromagnetic interactions through reorientation of the Cu(II) orbitals. We also present the structure of 1, 80 years after its synthesis was first reported.

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Slow Magnetization Relaxation in Unprecedented Mn^III₄Dy^III₃ and Mn^III₄Dy^III₅ Clusters from the Use of N-Salicylidene-o-aminophenol

Cited by 43 publications

References 24 publications

4f-Metal Clusters Exhibiting Slow Relaxation of Magnetization: A {Dy7} Complex with An Hourglass-like Metal Topology

4f-Metal Clusters Exhibiting Slow Relaxation of Magnetization: A {Dy7} Complex with An Hourglass-like Metal Topology

‘Metal Complexes as Ligands’ for the Synthesis of Coordination Polymers: A MnIII Monomer as a Building Block for the Preparation of an Unprecedented 1-D {MnIIMnIII}n Linear Chain

A Bridge Too Far: Testing the Limits of Polypyridyl Ligands in Bridging Soluble Subunits of a Coordination Polymer

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