Two novel Cu4O4 cubanes with functionalized chelating aziridine ligands

Putzien, Sophie; Wirth, Stefan; Roedel, J. Nicolas; Lorenz, Ingo‐Peter

doi:10.1016/j.poly.2011.02.004

Cited by 12 publications

(3 citation statements)

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“…The coordination chemistry of polynuclear copper(II) complexes has received much attention in the past decades due to their interesting architectures and potential applications in the fields of coordination polymers, magnetochemistry, bioinorganic chemistry, and catalysis . The inexpensive and commercially available multidentate amino alcohols have been broadly used for the preparation of polynuclear copper(II) complexes through a self-assembly process, since the hydroxyl groups of amino alcohols can be easily deprotonated in the presence of copper(II) salts and the resulting alkoxo groups act as a bridge leading to the formation of dimeric, dinuclear, trinuclear, tetranuclear, hexanuclear, octanuclear, and nonanuclear copper(II) clusters, coordination polymers, and supramolecular frameworks.…”

Section: Introductionmentioning

confidence: 99%

Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ₄-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study

et al. 2013

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The μ4-hydroxo- and alkoxo-bridged tetranuclear copper(II) complexes, [Cu4(μ4-OH)(dmae)4][Ag(NO3)4] (1), [Cu4(μ4-OH)(dmae)4][Na(NO3)4] (2), [Cu4(μ4-OH)(dmae)4][K(NO3)4] (3), and hexanuclear alkoxo-bridged "bicapped cubane" copper(II) complex [Cu6(ae)8(ClO4)2](ClO4)2·MeOH (8) (dmae = N,N-dimethylaminoethanolato and ae = 2-aminoethanolato) were synthesized via self-assembly from chelating amino alcohols and copper(II), silver (1), sodium (2), and potassium (3) nitrates or copper(II) perchlorate (8). The complexes are characterized by elemental analyses, single-crystal X-ray diffraction, and variable temperature magnetic measurements. The crystal structures of complexes 1-3 consist of almost planar tetranuclear [Cu4(μ4-OH)(dmae)4](3+) units, in which Cu(II) ions are also weakly bonded to nitrate anions. The adjacent tetranuclear units of 1-3 are connected by ionic interactions between nitrate anions and sodium, potassium, or silver cations resulting in the formation of 1D polymers. The crystal structure of 8 consists of hexanuclear [Cu6(ae)8](4+) "bicapped cubane" units, in which the capping Cu(II) ions are weakly bonded to perchlorate anions. The adjacent hexanuclear units of 8 are connected by hydrogen bonds resulting in the formation of 3D hydrogen bonded networks. Also the results from the synthetic studies leading to the formation of new copper(II) and silver(I) complexes (4-7) using Hae, 3-aminopropanol (Hap), and N,N-dimethylaminopropanol (Hdmap) in similar reactions, which gave tetra- and hexanuclear complexes, are presented. Experimental magnetic studies showed that complexes 1 and 2 exhibit dominant antiferromagnetic coupling leading to an S = 0 ground state, whereas 8 exhibits a large dominant antiferromagnetic interaction between the capping copper atoms and the copper atoms of the top and bottom faces of the cubane unit that define two isosceles triangles. This interaction leads to an S = 1/2 ground state for each triangle. The weak ferromagnetic interaction between these doublet states through the cubane unit leads to a triplet S = 1 ground state for 8. The values of the magnetic exchange coupling constant were the following: J = +1.8 (1) and +2.9 cm(-1) (2) between adjacent copper atoms; J' = -29.2 (1) and -32.2 cm(-1) (2) between opposite copper atoms; J = -297.6 cm(-1) and zJ' = +0.07 cm(-1) (8). Magnetic coupling constants calculated for 2 and 8 by DFT methods are in general of the same nature and magnitude as the experimental ones.

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Section: Introductionmentioning

confidence: 99%

Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ₄-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study

et al. 2013

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“…The equatorial angles differ greatly because of the steric demand of the chlorido ligand (N6-Cu1-Cl2 136.80(19)°, N8-Cu1-Cl2 126.67 (15) 4 ]. 75 The square planar azirine complex of palladium(II) 5d (Fig. 4) is slightly distorted because of the two different ligands, two chlorido ligands and two azirine-N atoms each in trans positions (N1-Pd1-N2 179.3(3)°, Cl1-Pd-Cl2 179.38(5)°).…”

Section: View Article Onlinementioning

confidence: 99%

“…in the tetrameric adamantane-analogous μ 4 -oxo-complex [(μ 4 -O)(μ 4 -Cl)(C 2 H 4 NHCu) 4 ]. 75 The square planar azirine complex of palladium(II) 5d (Fig. 4) is slightly distorted because of the two different ligands, two chlorido ligands and two azirine-N atoms each in trans positions (N1-Pd1-N2 179.…”

Section: Spectroscopic Characterizationmentioning

confidence: 99%

Synthesis, structural characterization, antimicrobial and cytotoxic effects of aziridine, 2-aminoethylaziridine and azirine complexes of copper(ii) and palladium(ii)

et al. 2012

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A Pair of Enantiopure Cubane‐Type Cu^II₄O₄ Clusters: Synthesis, Structure, Chirality and Magnetism

et al. 2014

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A pair of enantiopure cubane-type Cu II 4 O 4 clusters was constructed from simple chiral ligands (R or S)-2-[(2-hydroxy-1phenylethylimino)methyl]phenol (H 2 L R or S ). Single-crystal X-ray diffraction studies demonstrated that complexes 1R and 1S are enantiomers. They consist of a Cu II 4 O 4 cubane core in which the four Cu II centres are linked by a μ 3 -oxo bridge. The four Cu II ions in one cluster are all in a distorted square-pyramidal geometry. Circular dichroism (CD) spec-[a] Key

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Two novel Cu4O4 cubanes with functionalized chelating aziridine ligands

Cited by 12 publications

References 34 publications

Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ₄-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study

Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ₄-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study

Synthesis, structural characterization, antimicrobial and cytotoxic effects of aziridine, 2-aminoethylaziridine and azirine complexes of copper(ii) and palladium(ii)

A Pair of Enantiopure Cubane‐Type Cu^II₄O₄ Clusters: Synthesis, Structure, Chirality and Magnetism

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Two novel Cu4O4 cubanes with functionalized chelating aziridine ligands

Cited by 12 publications

References 34 publications

Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ4-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study

Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ4-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study

Synthesis, structural characterization, antimicrobial and cytotoxic effects of aziridine, 2-aminoethylaziridine and azirine complexes of copper(ii) and palladium(ii)

A Pair of Enantiopure Cubane‐Type CuII4O4 Clusters: Synthesis, Structure, Chirality and Magnetism

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Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ₄-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study

Structural Diversity due to Amino Alcohol Ligands Leading to Rare μ₄-Hydroxo-Bridged Tetranuclear and “Bicapped Cubane” Cores in Copper(II) Complexes: A Theoretical and Experimental Magnetostructural Study

A Pair of Enantiopure Cubane‐Type Cu^II₄O₄ Clusters: Synthesis, Structure, Chirality and Magnetism