A new CuII-dinuclear paddlewheel complex. Structural and electronic properties

Seguin, Ana Karina; Wrighton-Araneda, Kerry; Cortés‐Arriagada, Diego; Cruz, Carlos; Venegas‐Yazigi, Diego; Paredes-Garcı́a, Verónica

doi:10.1016/j.molstruc.2020.129172

Cited by 8 publications

(8 citation statements)

References 48 publications

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“…Regarding the spin density distribution, the Cu center displays values of 0.6 a.u. in agreement with other works related to the magnetic properties of Cu(II) complexes (showing one unpaired electron) [54,55] . Besides, the spin density surface (Fig.…”

Section: Spin Density and Magnetic Propertiessupporting

confidence: 93%

{{_{{\rm x}{^{2}}- {\rm y}{^{2}}}}}

orbitals as is proper of Cu(II) center in a square‐planar ligand field [42,49] .…”

Section: Isolated Copper Corroles and Graphene Nanosheet As A Platformsupporting

confidence: 90%

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Deciphering Electronic and Structural Effects in Copper Corrole/Graphene Hybrids**

Wrighton-Araneda

Cortés‐Arriagada

Dreyse

et al. 2023

Chemistry A European J

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Non-covalent hybrid materials based on graphene and A 3 -type copper corrole complexes were computationally investigated. The corroles 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 once the hybrid systems are held. The graphene-corrole hybrids displayed outstanding stability via the interplay of dispersion and electrostatic driving forces, while graphene act as an electron reservoir. The hybrid structures exposed an intriguing magneto-chemical performance, compared to the isolated counterparts, that evidenced how structural and electronic effects contributed to the magnetic response for both ferromagnetic and antiferromagnetic cases. Directional spin polarization and spin transfer from the corrole to the graphene surface participate in the amplification. Finally, there are relations between the spin transfer, the magnetic response, and the copper distorted ligand field, offering exciting hints about modulating the magnetic response. Therefore, this work shows that copper corroles emerged as versatile building blocks for graphene hybrid materials, especially in applications requiring a magnetic response.

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Section: Spin Density and Magnetic Propertiessupporting

confidence: 93%

{{_{{\rm x}{^{2}}- {\rm y}{^{2}}}}}

orbitals as is proper of Cu(II) center in a square‐planar ligand field [42,49] .…”

Section: Isolated Copper Corroles and Graphene Nanosheet As A Platformsupporting

confidence: 90%

Deciphering Electronic and Structural Effects in Copper Corrole/Graphene Hybrids**

Wrighton-Araneda

Cortés‐Arriagada

Dreyse

et al. 2023

Chemistry A European J

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“…Regarding the spin density distribution, the Cu center displays values of 0.6 a.u. in agreement with other works related to the magnetic properties of Cu(II) complexes (showing one unpaired electron) [67,81]. Besides, the spin density surface (Fig.…”

Section: Spin Density and Magnetic Propertiessupporting

confidence: 92%

“…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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“…On the other hand, the computational studies can complement the experimental evidence obtained by spectroscopic and magnetic studies using electronic structure descriptions. For instance, theoretical-experimental magnetic studies on molecular copper complexes and 1D copper coordination polymers − have successfully rationalized the nature and the magnitude of magnetic coupling constants by density functional theory (DFT) methods. ,,− With this in mind, DFT methods represent a powerful tool to rationalize the electronic structure of copper complexes.…”

Section: Introductionmentioning

confidence: 99%

Chiral 1D Metal–Organic Materials Based on Cu(II) and Amino Acid Schiff Bases

Cruz

González

Rubio

et al. 2021

Crystal Growth & Design

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Four new chiral coordination polymers (CPs), {[Cu(HL n )MeOH]•NO 3 } ∞ (n = 1−4), were obtained using a chiral building block synthesized from the condensation reaction of L-or D-valine with an imidazole aldehyde. These CPs crystallize in a noncentrosymmetric space group P2 1 2 1 2 1 , evidencing that the chirality of the α-amino acid valine is transferred to the structure of the coordination polymer. Moreover, the CPs present a 1D structure with a Cu(II) cation in a square base pyramid geometry formed by two units of chiral ligand and a methanol molecule. The magnetic measurement and theoretical calculations show that the Cu(II) spin carriers are magnetically communicated through the carboxylate bridge, presenting a 1D ferromagnetic chain behavior. Furthermore, four new stable molecular compounds [Cu(HL n )-DMSO] + (n = 1−4), sharing the same chiral building block of CPs, were characterized by circular dichroism (CD). The theoretical electronic excited states of the molecular compounds reproduce the CD experimental spectra showing that the intrinsic chiral activity of the α-amino acid Schiff base is transferred to the Cu(II) centers. Remarkably, using crystal engineering tools, a family of chiral coordination compounds was obtained and analyzed combining several experimental and theoretical approaches, leading to a robust understanding of its chemical and physical properties.

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A new CuII-dinuclear paddlewheel complex. Structural and electronic properties

Cited by 8 publications

References 48 publications

Deciphering Electronic and Structural Effects in Copper Corrole/Graphene Hybrids**

Deciphering Electronic and Structural Effects in Copper Corrole/Graphene Hybrids**

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

Chiral 1D Metal–Organic Materials Based on Cu(II) and Amino Acid Schiff Bases

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