Malonate-based copper(II) coordination compounds: ferromagnetic coupling controlled by dicarboxylates

Pasán, Jorge; Delgado, Fernando; Rodrı́guez-Martı́n, Yolanda; Hernández-Molina, Marı́a; Ruíz-Pérez, Catalina; Sanchiz, Joaquı́n; Lloret, Francesc; Julve, Miguel

doi:10.1016/s0277-5387(03)00203-1

Cited by 105 publications

(60 citation statements)

References 56 publications

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“…However, the magnetic couplings are weak enough to allow the nearby presence of the excited doublet states (see Figure 5) accounting for the observed thermal dependence of the magnetisation curves ( Figure 4). The ferromagnetic nature of the magnetic coupling can be attributed to the syn-anti conformation of the carbonato bridge (Figure 6 c), as known for other copper(II) complexes in which a carboxylate [17] or carbonate [8b,d-h,j,k,m,o,p, 18] group adopts the syn-anti conformation.…”

supporting

confidence: 60%

A Trinuclear Copper(II) Cryptate and Its μ₃‐CO₃ Cascade Complex: Thermodynamics, Structural and Magnetic Properties

Mateus

Delgado

Lloret

et al. 2011

Chemistry A European J

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The 2,4,6-triethylbenzene-capped hexaamine macrobicycle with pyridyl spacers (pyr) was able to coordinate three copper(II) ions within its cavity. Potentiometric studies performed at 298.2 K in MeOH/H(2)O (50:50 v/v) and at ionic strength 0.10 mol dm(-3) in KNO(3) revealed that trinuclear species predominate in solution from pH 5.0, the hydroxo complexes being the main species, which start forming at unusual very low pH values. The single-crystal X-ray determination of the trinuclear complex showed that the three copper centres have square-planar geometry, arranged in an almost equilateral triangle, and have carbonate bridging the three metal centres. The presence of carbonate resulted from fixation of atmospheric CO(2). The present study represents the first μ(3)-CO(3)-bridged trinuclear copper(II) complex located in the interior of a macrobicyclic cavity. The magnetic data of [Cu(3)(pyr)(μ(3)-CO(3))]·(ClO(4))(4) showed ferromagnetic intramolecular interactions [J=3.80 cm(-1), based on the Hamiltonian H=-J(S(1)S(2)+S(2)S(3)+S(1)S(3))] yielding a spin quartet, S=3/2, ground state. Density functional calculations on the experimental geometry of the trinuclear complex showed that the ferromagnetic nature of the magnetic coupling can be attributed to the syn-anti conformation of the carbonato bridge, and a magneto-structural correlation, based on the different conformations (syn-anti, syn-syn and anti-anti), is presented. The interesting properties observed, namely the lowering of the pK(a) of coordinated water molecules to unusual values and the good fit of the carbonate anion between the copper centres, derive from the special architecture of pyr.

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confidence: 60%

A Trinuclear Copper(II) Cryptate and Its μ₃‐CO₃ Cascade Complex: Thermodynamics, Structural and Magnetic Properties

Mateus

Delgado

Lloret

et al. 2011

Chemistry A European J

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“…The value of J for 1 is the largest one observed in the family of carboxylate(phenylmalonate)-bridged copper(II) complexes (J ranging from 20.59(1) to +4.44(5) cm 21 ) 9,17 and it is within the range of previously reported magnetic couplings of antisyn carboxylate(malonate)-bridged copper(II) complexes. 4 The smaller value of t of the copper atom in the case of 1 when compared to other examples with the phenylmalonate ligand reduces the admixture of the d z 2 character in the d x 2 2y 2 magnetic orbital and reinforces the magnetic coupling through the equatorial-equatorial exchange pathway, everything being similar. The weak antiferromagnetic interaction (ca.…”

mentioning

confidence: 88%

“…[4][5][6][7][8] In previous studies with these compounds, we have observed that the insertion of additional groups in the malonate skeleton (for instance, a phenyl group) modifies the supramolecular interactions and the dimensionality of the coordination polymer, but the ferromagnetic nature of the magnetic coupling is kept as in the compound [Cu(H 2 O) 3 ][Cu(Phmal) 2 ] (H 2 Phmal = phenylmalonic acid). 9 The use of potentially bridging nitrogen donor heterocycles as coligands has proved to be very appealing because of the construction of supramolecular motifs with varied functions.…”

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Metamagnetism in hydrophobically induced carboxylate (phenylmalonate)-bridged copper(ii) layers

et al. 2006

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Self-assembly of copper(II) ions, phenylmalonate and pyrimidine yields the layered compound [Cu(pym)(Phmal)] n (1) where intralayer ferro-and interlayer antiferromagnetic interactions occur with three-dimensional antiferromagnetic ordering at T c = 2.15 K.The construction of multidimensional magnetic materials with magnetic ordering is one of the major challenges in magnetochemistry. 1 For such a purpose, the construction of three-dimensional (3D) systems is a good approach, but a deep study of the nature and intensity of the coupling among the paramagnetic centres in these systems is precluded due to the lack of theoretical models to analyze the magnetic ordered state. On the other hand, interesting studies have been performed on 2D systems with different intraand interlayer magnetic interactions. 2,3 Previous studies by Kahn and co-workers in designing molecule-based magnets have shown that organizing ferromagnetic arrangements in extended 2D or 3D systems is quite a difficult task. 1 The choice of a specifically tailored building block is crucial in the design of systems with tunable dimensionality displaying ferromagnetic coupling.The malonate-bridged copper(II) complexes show a wide variety of molecular architectures which exhibit ferromagnetic coupling in most cases. [4][5][6][7][8] In previous studies with these compounds, we have observed that the insertion of additional groups in the malonate skeleton (for instance, a phenyl group) modifies the supramolecular interactions and the dimensionality of the coordination polymer, but the ferromagnetic nature of the magnetic coupling is kept as in the compound [Cu(H 2 O) 3 ][Cu(Phmal) 2 ] (H 2 Phmal = phenylmalonic acid). 9 The use of potentially bridging nitrogen donor heterocycles as coligands has proved to be very appealing because of the construction of supramolecular motifs with varied functions. [10][11][12][13] In the present work, we focus on the structure and variable-temperature magnetic study of the layered compound [Cu(pym)(Phmal)] n (1) (pym = pyrimidine) together with a brief analysis of the supramolecular effects that determine its twodimensional structure. The compound has a metamagnetic behaviour due to the coexistence of intralayer ferromagnetic and interlayer antiferromagnetic interactions, the critical magnetic field being H c = 130 G.

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“…For 1, the χ m T value at 300 K was 0.373 cm 3 ·K·mol -1 , close to the value expected for an uncoupled S = 1/2 spin with g = 2. [27] The data was fit to the standard Bleaney-Bowers Equation [Equation (1)] for a Heisenberg isotropic pair of S = 1/2 ions. [28] The best fit to the data ( Figure S8 …”

Section: Variable Temperature Magnetic Susceptibility Ofmentioning

confidence: 99%

Metal‐Dependent Topologies and Water Aggregations in Copper and Nickel Carboxycinnamate Coordination Polymers with a Long‐Spanning Dipyridylamide Ligand

Rogers

Glatz

LaDuca

2015

Zeitschrift anorg allge chemie

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Abstract. Hydrothermal reaction of the requisite metal nitrate, carboxycinnamic acid (H 2 cca), and the long-spanning dipyridylamide bis(4-pyridylformyl)piperazine (4-bpfp) generate crystalline coordination polymers whose topology depends critically on the metal coordination geometric preference. These two new phases were structurally characterized by single-crystal X-ray diffraction. {[Cu(cca)(4-bpfp)]·2.5H 2 O} n (1) manifests a non-interpenetrated 6-connected pcu net based on chain motifs featuring carboxylate-bridged {Cu 2 (OCO) 2 }

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Malonate-based copper(II) coordination compounds: ferromagnetic coupling controlled by dicarboxylates

Cited by 105 publications

References 56 publications

A Trinuclear Copper(II) Cryptate and Its μ₃‐CO₃ Cascade Complex: Thermodynamics, Structural and Magnetic Properties

A Trinuclear Copper(II) Cryptate and Its μ₃‐CO₃ Cascade Complex: Thermodynamics, Structural and Magnetic Properties

Metamagnetism in hydrophobically induced carboxylate (phenylmalonate)-bridged copper(ii) layers

Metal‐Dependent Topologies and Water Aggregations in Copper and Nickel Carboxycinnamate Coordination Polymers with a Long‐Spanning Dipyridylamide Ligand

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Malonate-based copper(II) coordination compounds: ferromagnetic coupling controlled by dicarboxylates

Cited by 105 publications

References 56 publications

A Trinuclear Copper(II) Cryptate and Its μ3‐CO3 Cascade Complex: Thermodynamics, Structural and Magnetic Properties

A Trinuclear Copper(II) Cryptate and Its μ3‐CO3 Cascade Complex: Thermodynamics, Structural and Magnetic Properties

Metamagnetism in hydrophobically induced carboxylate (phenylmalonate)-bridged copper(ii) layers

Metal‐Dependent Topologies and Water Aggregations in Copper and Nickel Carboxycinnamate Coordination Polymers with a Long‐Spanning Dipyridylamide Ligand

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A Trinuclear Copper(II) Cryptate and Its μ₃‐CO₃ Cascade Complex: Thermodynamics, Structural and Magnetic Properties

A Trinuclear Copper(II) Cryptate and Its μ₃‐CO₃ Cascade Complex: Thermodynamics, Structural and Magnetic Properties