Models to predict the magnetic properties of single- and multiple-bridged phosphate Cu<sup>II</sup> systems: a theoretical DFT insight

Muñoz‐Becerra, Karina; Aravena, Daniel; Ruiz, Eliseo; Spodine, Evgenia; Soto-Donoso, Nicolás; Paredes-Garcı́a, Verónica; Venegas‐Yazigi, Diego

doi:10.1039/c6qi00394j

Cited by 7 publications

(10 citation statements)

References 72 publications

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“…Indeed, the experimental value at 72 cm –1 is about 2 times larger than the DFT ones. Despite this, the overall picture is quite well represented and the DFT calculations presented here tend to validate the structural rationalization done by Mehrani et al The ferromagnetic and antiferromagnetic characters of both J 1 and J 2 couplings have been justified regarding the Cu–O–Cu angles of both pairs of magnetic centers and the empirical relationship of Hatfield. − Indeed, it has been observed a dependence of the exchange coupling in binuclear Cu(II) complexes bridged by hydroxo groups on the Cu–O–Cu angles, which tends to be antiferromagnetic for an angle greater than 97.5° and ferromagnetic otherwise. Regarding the antiferromagnetic J 1 coupling, both concerned Cu–O–Cu angles are at about 99°, while for the ferromagnetic J 2 couplings, they are at about 97° (see ref for further discussions).…”

Section: Resultssupporting

confidence: 76%

Consistent Evaluation of Magnetic Exchange Couplings in Multicenter Compounds in KS-DFT: The Recomposition Method

David

Ferré

Guennic

2022

J. Chem. Theory Comput.

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The use of broken-symmetry calculations in Kohn− Sham density functional theory has offered an affordable route to study magnetic exchange couplings in transition-metal-based compounds. However, computing this property in compounds exhibiting several couplings is still challenging and especially due to the difficulties to overcome the well-known problem of spin contamination. Here, we present a new and general method to compute magnetic exchange couplings in systems featuring several spin sites. To provide a consistent spin decontamination of J values, our strategy exploits the decomposition method of the magnetic exchange coupling proposed by Coulaud et al. and generalizes our previous work on diradical compounds where the overall magnetic exchange coupling is defined as the sum of its three main and properly extracted physical contributions (direct exchange, kinetic exchange, and spin polarization). In this aim, the generalized extraction of all contributions is presented to systems with multiple spin sites bearing one unpaired electron. This is done by proposing a new paradigm to treat the kinetic exchange contribution, which proceeds through monorelaxations of the magnetic orbitals. This method, so-called the recomposition method, is applied to a compound featuring three Cu(II) ions with a linear arrangement and to a recently synthesized complex containing a Cu 4 O 4 cubane unit presenting an unusual magnetic behavior.

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Section: Resultssupporting

confidence: 76%

Consistent Evaluation of Magnetic Exchange Couplings in Multicenter Compounds in KS-DFT: The Recomposition Method

David

Ferré

Guennic

2022

J. Chem. Theory Comput.

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“…Using the PHI software, [20] the temperature dependence of χT vs T curves for 2 and 3 were fitted. The presence of 1,3‐O−P−O phosphate bridges between the copper centres in complex 2 (Figure 4), is responsible for the observed antiferromagnetic interaction, as has been demonstrated by computational studies on previously reported X‐ray structures and magnetic data of dinuclear copper complexes [21] . Adaptation of this model for 2 results in very close agreement of the experimental data with fitted data yielding the values of J=−5.60 cm −1 , g=2.14, and χ TIP= 1.2×10 −4 cm 3 mol −1 (Figure 4).…”

Section: Resultssupporting

confidence: 61%

Nuclearity Control in Molecular Copper Phosphates Derived from a Bulky Arylphosphate: Synthesis, Structural and Magnetic Studies

Prapakaran

Sathish

et al. 2023

Eur J Inorg Chem

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Dedicated to Professor Dietmar Stalke on the occasion of his 65 th birthdayStarting from sterically encumbered 2,6-di-tert-butylphenyl phosphate (dtbppH 2 ) and co-ligand 3,5-dimethyl pyrazole (dmpz), it is possible to isolate either mono-, di-or tetranuclear copper phosphates by varying the copper source and making attendant changes in the reaction conditions. For example, reaction of copper nitrate with dtbppH 2 and dmpz at 60 °C leads to the isolation of the mononuclear copper phosphate [Cu(dtbppH) 2 (dmpz)(MeOH) 2 ] (1) as the only product. However, the use of copper acetate in place of copper nitrate and conducting the reaction at the room temperature leads to the formation of both dinuclear [Cu(dtbpp)(dmpz) 2 ] 2 (2) and tetranuclear [Cu 2 (dtbpp)(dmpz) 2 (OAc)(MeO)] 2 (3) from the same reaction mixture. Compounds 2 and 3 could be isolated in pure form through fractional crystallization. Copper phosphates 1-3 have been characterized by both analytical and spectroscopic methods including EPR and magnetic measurements. The molecular structures of all three compounds were established through single crystal diffraction studies. Dc magnetic measurements indicate antiferromagnetic interactions between the metal centres in all the compounds.

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“…Where H, J12, Ŝ1, and Ŝ2 are the spin Hamiltonian, the magnetic coupling constant between fragment 1 and 2, the spin operators for fragment 1, and the spin operator for fragment 2, respectively. The broken-symmetry approach with non-projected spin employed has been extensively used for transition metal complexes [63][64][65][66][67]. The J values were calculated as follows [68,69]…”

Section: Methodsmentioning

confidence: 99%

Augmented Magnetic Response and Spin-Transfer in Copper Corrole/Graphene Hybrids - A DFT Study

Wrighton-Araneda

Cortés‐Arriagada

Dreyse

et al. 2022

Preprint

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The search for hybrid materials with outstanding electronic performance is highly demanding Since copper corroles have emerged as versatile building blocks providing outstanding electronic, and reactivity properties, a new series of non-covalent hybrid materials were computationally investigated based on pristine graphene and A3-type copper corrole complexes. The corrole complexes contain strong electron-withdrawing fluorinated substituents at the meso positions. Our results show that the non-innocent character of corrole moiety modulates the structural, electronic, and magnetic properties of the hybrid systems. The graphene-corrole hybrids display outstanding stability via the interplay of dispersion and electrostatic driving forces while graphene act as an electron reservoir for more conductive cases. Furthermore, the hybrid structures display an intriguing magneto-chemical performance since a detailed analysis of magnetic properties evidence how structural and electronic changes contribute to the amplification of the magnetic response also for ferromagnetic and antiferromagnetic cases. This amplification is accompanied by the spin transfer which characterized by a directional spin polarization from the corrole through the graphene surface. Main results suggest that graphene-corrole hybrids are excellent candidates for technologic applications due to the ferromagnetic tendency, the augmented magnetic response, the tunability due to substituents, and the potential conductive properties. Finally, a statistical analysis of magnetic properties suggests correlations between spin transfer, augmented magnetic response, and the geometrical distortion of the copper ligand field, offering exciting hints about how to modulate the magnetic response in the studied hybrid systems.

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Models to predict the magnetic properties of single- and multiple-bridged phosphate Cu^II systems: a theoretical DFT insight

Abstract: Models for the 1,1 and 1,3-bridging modes of phosphate for copper(ii) compounds were developed. Using unrestricted corresponding orbitals (UCO), a graphical identification of the predominant exchange pathway was described.

Cited by 7 publications

References 72 publications

Consistent Evaluation of Magnetic Exchange Couplings in Multicenter Compounds in KS-DFT: The Recomposition Method

Consistent Evaluation of Magnetic Exchange Couplings in Multicenter Compounds in KS-DFT: The Recomposition Method

Nuclearity Control in Molecular Copper Phosphates Derived from a Bulky Arylphosphate: Synthesis, Structural and Magnetic Studies

Augmented Magnetic Response and Spin-Transfer in Copper Corrole/Graphene Hybrids - A DFT Study

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Models to predict the magnetic properties of single- and multiple-bridged phosphate CuII systems: a theoretical DFT insight

Abstract: Models for the 1,1 and 1,3-bridging modes of phosphate for copper(ii) compounds were developed. Using unrestricted corresponding orbitals (UCO), a graphical identification of the predominant exchange pathway was described.

Cited by 7 publications

References 72 publications

Consistent Evaluation of Magnetic Exchange Couplings in Multicenter Compounds in KS-DFT: The Recomposition Method

Consistent Evaluation of Magnetic Exchange Couplings in Multicenter Compounds in KS-DFT: The Recomposition Method

Nuclearity Control in Molecular Copper Phosphates Derived from a Bulky Arylphosphate: Synthesis, Structural and Magnetic Studies

Augmented Magnetic Response and Spin-Transfer in Copper Corrole/Graphene Hybrids - A DFT Study

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Models to predict the magnetic properties of single- and multiple-bridged phosphate Cu^II systems: a theoretical DFT insight