Triangular {Ni3} coordination cluster with a ferromagnetically coupled metal-ligand core

Schmitz, Sebastian; Leusen, Jan van; Izarova, Natalya V.; Bourone, Svenja; Ellern, Arkady; Kögerler, Paul; Monakhov, Kirill Yu.

doi:10.1016/j.poly.2018.01.014

Cited by 7 publications

(7 citation statements)

References 24 publications

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“…This triangular feature has already been observed in the literature [45]. The observation of triangles with paramagnetic metallic ions is well documented [46,47], leading to high spin molecules presenting either ferromagnetic or antiferromagnetic interactions, depending on the geometric parameters.…”

Section: Co3(h2o)(dmf)2-(2-2h)-3 Ni3(h2o)(dmf)2-(2-2h)-3 Zn3(h2o)(dmfsupporting

confidence: 68%

Formation of Unsymmetrical Trinuclear Metallamacrocycles Based on Two Different Cone Calix[4]arene Macrocyclic Rings

et al. 2020

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A combination of tetrasulfonylcalix[4]arene (3-4H) together with a calix[4]arene dicarboxylate derivative 2-4H led, in the presence of MII(NO3)2 (M = Co, Ni, Zn), to the formation of three novel isostructural metallomacrocycles of formula [M3(DMF)2(μ3-H2O)-(2-2H)-3]. The structure of the prepared coordination compounds was studied in the solid state using single crystal/powder X-ray diffraction studies. The X-ray diffraction on single crystal revealed that the structure of the obtained supramolecular complexes is composed of a trinuclear metallic cluster [M3]+6 held between one di-deprotonated molecule of (2-2H)2− offering two carboxylate groups for binding metal cations and one tetra-deprotonated compound 34−, where four oxygen atoms, belonging to four deprotonated phenolic moieties and three oxygen atoms coming from three SO2 groups, are coordinated with the cluster core. Thus, an example of an easily reproducible molecular recognition pattern involving two different types of calix[4]arene based ligands, displaying different coordination moieties, and trinuclear metallic clusters, is reported here. In addition, it has been shown that the cone moieties of the calixarene also encapsulate solvent molecules.

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Section: Co3(h2o)(dmf)2-(2-2h)-3 Ni3(h2o)(dmf)2-(2-2h)-3 Zn3(h2o)(dmfsupporting

confidence: 68%

Formation of Unsymmetrical Trinuclear Metallamacrocycles Based on Two Different Cone Calix[4]arene Macrocyclic Rings

et al. 2020

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“…HL·SMe was first immobilized in the form of SAMs on a Au surface from a 1.0 mmol ethanolic solution to assess the structural integrity of the uncoordinated, charge-neutral ligand on the solid substrate. As the comparison of the Fourier transform infrared (FT-IR) and FT-IRRAS spectra of HL·SMe (see Supporting Information) indicates that its chemical structure remains effectively unchanged upon adsorption, we subjected complexes 1 – 4 to IRRAS analysis. Although a small shift of the recorded IR vibrational bands is observed due to the presence of different Ln 3+ ions in the respective compounds and thereby the resulting change in bond strengths, which is directly linked to the vibration frequency, the FT-IR spectra of 1 – 4 are nearly identical, as expected for these quasi-isostructural complexes (see Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) Complexes

et al. 2018

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A series of isostructural dinuclear 3d-4f complexes, isolated as [CuLn(L·SMe)(OOCMe)(NO)]· xMeOH (Ln = Gd 1, Tb 2, Dy 3, and Y 4; x = 0.75-1) and comprising one acetate and two thioether-Schiff base (L·SMe) bridging ligands based on 4-(methylthio)aniline and 2-hydroxy-3-methoxybenzaldehyde (HL·SMe = CHNOS), was synthesized and fully characterized. The magnetic properties of the charge-neutral {CuLn} complexes are dominated by ferromagnetic Cu-Ln exchange interactions. Large-area electron transport studies reveal that the average conductivity of robust, self-assembled {CuLn} monolayers on a gold substrate is significantly lower than that of common alkanethiolates. Theoretical calculations of transmission spectra of individual complexes 1 and 4 embedded between two metallic electrodes show that the molecular current-voltage ( I- V) characteristics are strongly influenced by electron transport through the Cu centers and thus fully independent of the lanthanide ion, in excellent agreement with the experimental I- V data for 1-4. The β-polarized transmission indicated by calculations of 1 and 4 points out their potential as spin filters. In addition, the reactivity of the title compound 1 with Cu in a square-pyramidal coordination environment toward methanolate and azide was examined, resulting in the formation of a linear trinuclear complex, [CuNa(L·SMe)]NO·3MeOH (5), characterized by antiferromagnetic exchange interactions between the two copper ions.

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“…The present study is motivated by the appealing electron transport features and the Kondo effect (Yan and Seminario, 2005; Parks et al, 2010) of mononuclear complexes of an octahedrally coordinated cobalt ion attached to gold electrodes via thiol bonds. The augmentation of our polynuclear complexes with ancillary groups like thioethers (Dreiser et al, 2015; Schmitz et al, 2018c) aims to contribute to their conformational and charge stabilization on metallic surfaces and, furthermore, to reduce their possible agglomeration due to steric repulsion between the structurally exposed –SR anchor points. It is however noteworthy that metal complexes derivatized by thiane functionalities as, for example, mononuclear copper(II) pyridyl–alcohol complexes are capable of featuring close intermolecular S···S contacts in the crystal lattice (Schmitz et al, 2019).…”

Section: Introductionmentioning

confidence: 99%

Conductive Self-Assembled Monolayers of Paramagnetic {CoIICo4III} and {Co4IICo2III} Coordination Clusters on Gold Surfaces

et al. 2019

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Two polynuclear cobalt(II,III) complexes, [Co5(N3)4(N-n-bda)4(bza·SMe)2] (1) and [Co6(N3)4(N-n-bda)2(bza·SMe)5(MeOH)4]Cl (2), where Hbza·SMe = 4-(methylthio)benzoic acid and N-n-H2bda = N-n-butyldiethanolamine, were synthesized and fully characterized by various techniques. Compound 1 exhibits an unusual, approximately C2-symmetric {CoIICo4III} core of two isosceles Co3 triangles with perpendicularly oriented planes, sharing a central, high-spin CoII ion residing in a distorted tetrahedral coordination environment. This central CoII ion is connected to four outer, octahedrally coordinated low-spin CoIII ions via oxo bridges. Compound 2 comprises a semi-circular {Co4IICo2III} motif of four non-interacting high-spin CoII and two low-spin CoIII centers in octahedral coordination environments. Self-assembled monolayers (SAMs) of 1 and 2 were physisorbed on template-stripped gold surfaces contacted by an eutectic gallium-indium (EGaIn) tip. The acquired current density-voltage (I-V) data revealed that the cobalt-based SAMs are more electrically robust than those of the previously reported dinuclear {CuIILnIII} complexes with Ln = Gd, Tb, Dy, or Y (Schmitz et al., 2018a). In addition, between 170 and 220°C, the neutral, mixed-valence compound 1 undergoes a redox modification, yielding a {Co5}-based coordination cluster (1-A) with five non-interacting, high-spin octahedral CoII centers as indicated by SQUID magnetometry analysis in combination with X-ray photoelectron spectroscopy and infrared spectroscopy. Solvothermal treatment of 1 results in a high-nuclearity coordination cluster, [Co10(N3)2(N-n-bda)6(bza·SMe)6] (3), containing 10 virtually non-interacting high-spin CoII centers.

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Triangular {Ni3} coordination cluster with a ferromagnetically coupled metal-ligand core

Cited by 7 publications

References 24 publications

Formation of Unsymmetrical Trinuclear Metallamacrocycles Based on Two Different Cone Calix[4]arene Macrocyclic Rings

Formation of Unsymmetrical Trinuclear Metallamacrocycles Based on Two Different Cone Calix[4]arene Macrocyclic Rings

Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) Complexes

Conductive Self-Assembled Monolayers of Paramagnetic {CoIICo4III} and {Co4IICo2III} Coordination Clusters on Gold Surfaces

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