Three Cluster Organic Frameworks Constructed from Tetranuclear Cluster Units: Structure and Properties

Three novel tetranuclear copper(II) complexes namely [Cu4(L 1)4]•(dmf) (1), [Cu4(L 1)4] (2) and [Cu4(L 2)2(HL 2)2(H2O)2]•2(ClO4)•6(H2O) (3) (H2L 1 , (E)-2-((1-hydroxybutan-2ylimino)methyl)phenol; H2L 2 , (E)-2-((1-hydroxybutan-2-ylimino)methyl)-6-methoxyphenol)) were synthesised from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligands. The structural determination reveals that complex 1 crystallizes in the monoclinic system with space group C2/c, whereas both the complexes 2 and 3 crystallize in the triclinic system with space group P-1. Complexes 1 and 2 possess face-sharing dicubane core, on the other hand complex 3 has double open cubane core structure. The copper(II) ions in the cubane core are in distorted square planar geometries, and weak π…π and C-H…π interactions lead to formation of a 2D supramolecular architecture for complexes 1 and 2. At room temperature complexes 1, 2 and 3, exhibit fluorescence with a quantum yield (Φs) of 0.47, 0.49 and 0.38, respectively. Variable temperature magnetic susceptibility measurements in the range 2-300 K indicate an overall weak antiferromagnetic exchange coupling in all complexes. The PHI program was used to study their magnetic behaviour. In agreement with their face-sharing dicubane structure, a Hamiltonian of the type H =-J1(S1S2+S1S2'+S1'S2+S1'S2')-J2S1S1', where S1 = S1' = S2 = S2' = SCu = 1/2, was used for studying complexes 1 and 2. Simulations performed suggest magnetic exchange constants with values close to J1 =-20 cm-1 and J2 = 0 cm-1 for these complexes. On the other hand, the spin Hamiltonian H =-J1(S1S4+S2S3)-J2(S1S3+S2S4)-J3S1S2, where S1 = S2 = S3 = S4 = SCu = 1/2, was used to study the magnetic behaviour of the double open cubane core of complex 3 and a good agreement between the experimental and simulated results was found by using the parameters g1 = g2 = 2.20, g3 = g4 = 2.18, J1 =-36 cm-1 , J2 =-44 cm-1 and J3 = 0 cm-1 .

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Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework

Paul

Bertolasi

Figuerola

et al. 2017

Journal of Solid State Chemistry

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Four 3D coordination polymers based on layers with single syn–anti carboxylate bridges: synthesis, structures, and magnetic properties

et al. 2018

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Three Cluster Organic Frameworks Constructed from Tetranuclear Cluster Units: Structure and Properties

Cited by 2 publications

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Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework

Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework

Four 3D coordination polymers based on layers with single syn–anti carboxylate bridges: synthesis, structures, and magnetic properties

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