Solvent switchable Cu<sup>II</sup> complexes

Borisova, Nataliya E.; Kostin, Andrey; Magdesieva, Tatiana V.; Reshetova, M. D.; Nikitin, Oleg M.; Paredes-Garcı́a, Verónica; Garland, M. T.; Hermosilla-Ibáñez, Patricio; Cañón‐Mancisidor, Walter; Rodionov, А. N.; Venegas‐Yazigi, Diego; Spodine, Evgenia

doi:10.1039/c3nj00722g

Cited by 11 publications

(4 citation statements)

References 42 publications

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“…5)is obtained with g = 2.15 and J = -397 cm -1. Such a strong antiferromagnetic spin-coupling involving two dx 2 -y 2 orbitals of the metal centers could be expected owing to magnetic interactions mediated by equatorial-equatorial bridging ligands with a Cu-O-Cu angle of 102.95(6)°[8,[13][14][15], agreeing well with those reported for other analogous compounds[19,20].…”

supporting

confidence: 87%

“…1 and 2, while selected bond lengths and angles are listed in Table 3. Compound 1 crystallizes in the monoclinic system with space group P2 1 /c, while complex [19,20,24,48,49]. By contrast, the binuclear unit of 2 exhibits two pentacoordinated Cu(II) centers in a square pyramidal (4+1) coordination geometry (Fig.…”

Section: Description Of the Molecular And Crystal Structuresmentioning

confidence: 99%

“…And it is now established that the major factor controlling the singlet-triplet energy gap, J, between the metal centers is the Cu-O-Cu angle [8,[13][14][15]. Di-copper(II) derivatives are also of importance as precursors in the chemistry of supramolecular [16] and discrete molecular highnuclearity copper(II) complexes [17][18][19][20][21].…”

Section: Introductionmentioning

confidence: 99%

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Doubly phenoxide-bridged binuclear copper(II) complexes with ono tridentate schiff base ligand: Synthesis, structural, magnetic and theoretical studies

et al. 2015

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International audienceThe tridentate ONO-donor Schiff base ligand H2L, derived from the condensation of 1-anisyl-1,3-butanedione and 2-aminophenol, was generated in situ and reacted with Cu(NO3)2*3H2O to yield two doubly phenoxo bridged di-copper(II) complexes depending on the nitrogenous base used. [Cu2L2] (1) is obtained in 85% and 75% yield in the presence of pyridine or 4-picoline, respectively, and [(py-tBu)2Cu2L2] (2) is isolated in 75% yield in the presence of 4-tert-butylpyridine. Compounds 1 and 2 were characterized in the solid-state by elemental analysis and FT-IR spectroscopy. Single crystal X-ray diffraction study reveals that in 1 the two four-coordinated copper atoms adopt a square planar geometry, whereas in 2 each Cu(II) metal ion shows a five coordinate square pyramidal (ONO,N + O) geometry. In each dimer, two μ-phenolic oxygen atoms bridge the two half-units forming a planar Cu2O2 core. EPR studies in fluid solutions indicate that the dimeric structure of 1 and 2 is destroyed upon dissolution. In the solid-state, 1 is EPR silent, whereas 2 presents an unresolved broad resonance (ΔH peak-to-peak = 71.5 G) with g = 2.071 at 298 K, along with the triplet state (S = 1) signature at g = 4.181. Variable temperature (2-300 K) magnetic susceptibility measurements exhibit strong antiferromagnetic interactions between the Cu(II) centers with a J value of −397 cm−1 for 1, while no interaction operates between the two spins localized on Cu(II) metal ions in 2. Ab initio calculations were also performed to supplement the experimental results

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supporting

confidence: 87%

Section: Description Of the Molecular And Crystal Structuresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Doubly phenoxide-bridged binuclear copper(II) complexes with ono tridentate schiff base ligand: Synthesis, structural, magnetic and theoretical studies

et al. 2015

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“…The spin density for Cu(II) centers reach values of up to 0.6 unpaired electrons, consistent with the reported values in related systems. 71,101 On the other hand, the delocalized spin density distribution quenches the magnetic coupling between unpaired electrons, and the nuclear spin of copper centers, explaining the less resolved hyperfine structure of the EPR spectrum. 6a and S9).…”

Section: Experimental and Computational Methodsmentioning

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 Tetranuclear copper(II) Complex with a Pyridine‐2,6‐dicarboxamide Ligand: Structural and Magnetic Properties and In vitro Antiproliferative Activity Against Human Cancer Cells

Mondal,

Saha,

Das

et al. 2024

ChemistrySelect

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A pentadentate diamide ligand, N,N′‐di(pyridine‐2‐yl)pyridine‐2,6‐dicarboxamide (L1H2) and its tetranuclear Cu(II) complex [Cu4(L1)2(μ3‐OH)2(H2O)3(ClO4)](ClO4) ⋅ H2O are reported. X‐ray crystal structure of the complex reveals that it has an open‐book type architecture. Two central copper atoms are connected to each other by two hydroxo bridges. Each of these two hydroxo bridges also connects the two central copper atoms to one of the two terminal copper atoms. Variable temperature susceptibility measurements show that χMT decreases with the temperature, indicating a strong antiferromagnetic behavior. With the help of DFT calculations the magnetic data was analyzed using the spin Hamiltonian H=−2 J1S3 ⋅ S4 −2 J2(S3 ⋅ S1+ S3 ⋅ S2+ S4 ⋅ S1+ S4 ⋅ S2)−2 J3S1 ⋅ S2 (where subscripts 1 and 2 refer to the terminal copper atoms and 3 and 4 refer to the central copper atoms). The best fit was obtained with 2 J1=−322 cm−1, 2 J2=+34.8 cm−1, 2 J3=−8.8 cm−1 and g=2.18, indicating a δ‐type interaction between terminal copper atoms. The complex proves to be an avid binder of ct‐DNA, with apparent binding constant (Kapp) value estimated as 1.536×107 M−1. In vitro experiments indicate that the Cu(II) complex reduced the proliferation of HCT116 cells among other cell lines. This reduction of cell proliferation may be attributed to the enhancement of intracellular ROS, along with modulation and disruption of cell cycle associated proteins. SKC conceptualized the project, arranged funding and involved in overall coordination among collaborators, analyzing the data, and writing the paper. AM was involved in doing the experimental work on synthesis of the compounds, carrying out analytical and spectroscopic measurements, collecting X‐ray crystallographic data and DNA binding experiments. MS, SM and KDS were involved in study of anticancer activities of the complex. SS helped in refining X‐ray structure of the complex. MC did the magnetic measurements and analysis whereas AF did the DFT calculations.

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Solvent switchable Cu^II complexes

Abstract: Dinuclear/tetranuclear interconversion of a magnetically coupled copper(ii) Schiff base complex driven by water rich solvents.

Cited by 11 publications

References 42 publications

Doubly phenoxide-bridged binuclear copper(II) complexes with ono tridentate schiff base ligand: Synthesis, structural, magnetic and theoretical studies

Doubly phenoxide-bridged binuclear copper(II) complexes with ono tridentate schiff base ligand: Synthesis, structural, magnetic and theoretical studies

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

A Tetranuclear copper(II) Complex with a Pyridine‐2,6‐dicarboxamide Ligand: Structural and Magnetic Properties and In vitro Antiproliferative Activity Against Human Cancer Cells

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Solvent switchable CuII complexes

Abstract: Dinuclear/tetranuclear interconversion of a magnetically coupled copper(ii) Schiff base complex driven by water rich solvents.

Cited by 11 publications

References 42 publications

Doubly phenoxide-bridged binuclear copper(II) complexes with ono tridentate schiff base ligand: Synthesis, structural, magnetic and theoretical studies

Doubly phenoxide-bridged binuclear copper(II) complexes with ono tridentate schiff base ligand: Synthesis, structural, magnetic and theoretical studies

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

A Tetranuclear copper(II) Complex with a Pyridine‐2,6‐dicarboxamide Ligand: Structural and Magnetic Properties and In vitro Antiproliferative Activity Against Human Cancer Cells

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Solvent switchable Cu^II complexes