Journal article
Supramolecular Maleate Adducts of Copper(II) 12-Metallacrown-4: Magnetism, EPR, and Alcohol Sorption Properties
European journal of inorganic chemistry, v 2017(41), pp 4866-4878
09 Nov 2017
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Abstract
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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Details
- Title
- Supramolecular Maleate Adducts of Copper(II) 12-Metallacrown-4: Magnetism, EPR, and Alcohol Sorption Properties
- Creators
- Anna V. Pavlishchuk - Taras Shevchenko National University of KyivSergey V. Kolotilov - L.V. Pisarzhevskii Institute of Physical ChemistryMatthias Zeller - Purdue University West LafayetteSamuel E. Lofland - Rowan UniversityMikhail A. Kiskin - NS Kurnakova Institute of General and Inorganic ChemistryNikolay N. Efimov - NS Kurnakova Institute of General and Inorganic ChemistryElena A. Ugolkova - NS Kurnakova Institute of General and Inorganic ChemistryVadim V. Minin - NS Kurnakova Institute of General and Inorganic ChemistryVladimir M. Novotortsev - NS Kurnakova Institute of General and Inorganic ChemistryAnthony W. Addison - Drexel University
- Publication Details
- European journal of inorganic chemistry, v 2017(41), pp 4866-4878
- Publisher
- Wiley
- Number of pages
- 13
- Grant note
- 12-03-90913 / Russian Foundation of Basic Research; Russian Foundation for Basic Research (RFBR) College of Arts & Sciences of Drexel University 0088-2014-0001 / Federal Agency of Scientific Organizations of Russia 0087210 / National Science Foundation (NSF) 1625543 / Division Of Chemistry; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS) CAP-491 / Ohio Board of Regents Grant 611488 / European Community's Seventh Framework Programme (FP7) Youngstown State University CHE 1625543 / National Science Foundation Major Research Instrumentation (NSF-MRI) grant
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000414919100008
- Scopus ID
- 2-s2.0-85033384874
- Other Identifier
- 991019168431204721
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- Collaboration types
- Domestic collaboration
- International collaboration
- Web of Science research areas
- Chemistry, Inorganic & Nuclear