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Supramolecular Maleate Adducts of Copper(II) 12-Metallacrown-4: Magnetism, EPR, and Alcohol Sorption Properties
Journal article   Peer reviewed

Supramolecular Maleate Adducts of Copper(II) 12-Metallacrown-4: Magnetism, EPR, and Alcohol Sorption Properties

Anna V. Pavlishchuk, Sergey V. Kolotilov, Matthias Zeller, Samuel E. Lofland, Mikhail A. Kiskin, Nikolay N. Efimov, Elena A. Ugolkova, Vadim V. Minin, Vladimir M. Novotortsev and Anthony W. Addison
European journal of inorganic chemistry, v 2017(41), pp 4866-4878
09 Nov 2017

Abstract

Chemistry Chemistry, Inorganic & Nuclear Physical Sciences Science & Technology
With maleate, [Cu-5(ahpha)(4)](2+) gives two complexes, [Cu-5(ahpha)(4)(DMF)(2)](MalH)(2)2DMF (1) and [Cu-5(ahpha)(4)(MalH)(2)] (2) (ahpha(2-) is 3-amino-3-hydroximinopropane hydroxamate; MalH(2) is maleic acid). Both 1 and 2 contain non-oligomerized [Cu-5(ahpha)(4)](2+) metallacrown blocks; in 1, two MalH(-) are bound to [Cu-5(ahpha)(4)](2+) only via H-bonds, while in 2, they coordinate to Cu2+. The X-band EPR of 1 was observed at 20 K, 100 K, and 295 K. The EPR at 20 K was of an S = 1/2 ground state, while at room temperature anisotropic |M-s| = 1 and |M-s| = 2 resonances around 3200 G (g approximate to 2.19) and 1600 G (g approximate to 4.25) were observed for the Cu-5 system, due to partial occupation of an S = 3/2 state. The room temperature EPR of 1 was simulated as the weighted sum of the spectra of its various S = 1/2, 3/2, and 5/2 states. Its magnetic behavior was fitted with a T-M vs. T model using a spin Hamiltonian accounting for central-peripheral (J(1)), peripheral-peripheral (J(2)) Cu2+-Cu2+ and intercrown (zJ) spin interactions, yielding J(1) = -156(4) cm(-1), J(2) = -63(1) cm(-1), and zJ = -4.5(3) cm(-1). For sorption of methanol and ethanol vapors at 293 K by a desolvated polycrystalline sample of 1, the shape of the adsorption and desorption isotherms indicated a gates opening phenomenon.

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Chemistry, Inorganic & Nuclear
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