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; Anthony W. Addison

doi:10.1002/ejic.201700976

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, Anthony W. Addison

Physics

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12 Scopus citations

Abstract

With maleate, [Cu₅(ahpha)₄]²⁺ gives two complexes, [Cu₅(ahpha)₄(DMF)₂](MalH)₂·2DMF (1) and [Cu₅(ahpha)₄(MalH)₂] (2) (ahpha^2– is 3-amino-3-hydroximinopropane hydroxamate; MalH₂ is maleic acid). Both 1 and 2 contain non-oligomerized [Cu₅(ahpha)₄]²⁺ metallacrown blocks; in 1, two MalH^– are bound to [Cu₅(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 |ΔM_s| = 1 and |ΔM_s| = 2 resonances around 3200 G (g ≈ 2.19) and 1600 G (g ≈ 4.25) were observed for the Cu₅ 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 χ_MT vs. T model using a spin Hamiltonian accounting for central–peripheral (J₁), peripheral–peripheral (J₂) Cu²⁺–Cu²⁺ and intercrown (zJ′) spin interactions, yielding J₁ = –156(4) cm^–1, J₂ = –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.

Original language	English (US)
Pages (from-to)	4866-4878
Number of pages	13
Journal	European Journal of Inorganic Chemistry
Volume	2017
Issue number	41
DOIs	https://doi.org/10.1002/ejic.201700976
State	Published - Nov 9 2017

All Science Journal Classification (ASJC) codes

Inorganic Chemistry

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10.1002/ejic.201700976

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Pavlishchuk, A. V., Kolotilov, S. V., Zeller, M., Lofland, S. E., Kiskin, M. A., Efimov, N. N., Ugolkova, E. A., Minin, V. V., Novotortsev, V. M., & Addison, A. W. (2017). Supramolecular Maleate Adducts of Copper(II) 12-Metallacrown-4: Magnetism, EPR, and Alcohol Sorption Properties. European Journal of Inorganic Chemistry, 2017(41), 4866-4878. https://doi.org/10.1002/ejic.201700976

@article{59a8b6b24e01443e8dfef4e8384a2448,

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

abstract = "With maleate, [Cu5(ahpha)4]2+ gives two complexes, [Cu5(ahpha)4(DMF)2](MalH)2·2DMF (1) and [Cu5(ahpha)4(MalH)2] (2) (ahpha2– is 3-amino-3-hydroximinopropane hydroxamate; MalH2 is maleic acid). Both 1 and 2 contain non-oligomerized [Cu5(ahpha)4]2+ metallacrown blocks; in 1, two MalH– are bound to [Cu5(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 |ΔMs| = 1 and |ΔMs| = 2 resonances around 3200 G (g ≈ 2.19) and 1600 G (g ≈ 4.25) were observed for the Cu5 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 χMT vs. T model using a spin Hamiltonian accounting for central–peripheral (J1), peripheral–peripheral (J2) Cu2+–Cu2+ and intercrown (zJ′) spin interactions, yielding J1 = –156(4) cm–1, J2 = –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.",

author = "Pavlishchuk, {Anna V.} and Kolotilov, {Sergey V.} and Matthias Zeller and Lofland, {Samuel E.} and Kiskin, {Mikhail A.} and Efimov, {Nikolay N.} and Ugolkova, {Elena A.} and Minin, {Vadim V.} and Novotortsev, {Vladimir M.} and Addison, {Anthony W.}",

note = "Funding Information: A. V. P. thanks the Russian Foundation of Basic Research (grant no. 12-03-90913) and the European Community's Seventh Framework Programme (FP7/2007-2013, grant agreement no. 611488). M. A. K., N. N. E., E. A. U., V. V. M., and V. M. N. acknowledge the Federal Agency of Scientific Organizations of Russia (project 0088-2014-0001) for financial support. A. W. A. thanks the College of Arts & Sciences of Drexel University for support. We thank Mr. T. Wade for skilled support for the ESI-MS analyses. The X-ray diffractometers were funded by National Science Foundation (NSF) grant 0087210, Ohio Board of Regents Grant CAP-491, Youngstown State University, and National Science Foundation Major Research Instrumentation (NSF-MRI) grant CHE 1625543. Publisher Copyright: {\textcopyright} 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2017",

month = nov,

day = "9",

doi = "10.1002/ejic.201700976",

language = "English (US)",

volume = "2017",

pages = "4866--4878",

journal = "Berichte der deutschen chemischen Gesellschaft",

issn = "0365-9496",

publisher = "Wiley-VCH Verlag",

number = "41",

}

TY - JOUR

T1 - Supramolecular Maleate Adducts of Copper(II) 12-Metallacrown-4

T2 - Magnetism, EPR, and Alcohol Sorption Properties

AU - Pavlishchuk, Anna V.

AU - Kolotilov, Sergey V.

AU - Zeller, Matthias

AU - Lofland, Samuel E.

AU - Kiskin, Mikhail A.

AU - Efimov, Nikolay N.

AU - Ugolkova, Elena A.

AU - Minin, Vadim V.

AU - Novotortsev, Vladimir M.

AU - Addison, Anthony W.

N1 - Funding Information: A. V. P. thanks the Russian Foundation of Basic Research (grant no. 12-03-90913) and the European Community's Seventh Framework Programme (FP7/2007-2013, grant agreement no. 611488). M. A. K., N. N. E., E. A. U., V. V. M., and V. M. N. acknowledge the Federal Agency of Scientific Organizations of Russia (project 0088-2014-0001) for financial support. A. W. A. thanks the College of Arts & Sciences of Drexel University for support. We thank Mr. T. Wade for skilled support for the ESI-MS analyses. The X-ray diffractometers were funded by National Science Foundation (NSF) grant 0087210, Ohio Board of Regents Grant CAP-491, Youngstown State University, and National Science Foundation Major Research Instrumentation (NSF-MRI) grant CHE 1625543. Publisher Copyright: © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2017/11/9

Y1 - 2017/11/9

N2 - With maleate, [Cu5(ahpha)4]2+ gives two complexes, [Cu5(ahpha)4(DMF)2](MalH)2·2DMF (1) and [Cu5(ahpha)4(MalH)2] (2) (ahpha2– is 3-amino-3-hydroximinopropane hydroxamate; MalH2 is maleic acid). Both 1 and 2 contain non-oligomerized [Cu5(ahpha)4]2+ metallacrown blocks; in 1, two MalH– are bound to [Cu5(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 |ΔMs| = 1 and |ΔMs| = 2 resonances around 3200 G (g ≈ 2.19) and 1600 G (g ≈ 4.25) were observed for the Cu5 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 χMT vs. T model using a spin Hamiltonian accounting for central–peripheral (J1), peripheral–peripheral (J2) Cu2+–Cu2+ and intercrown (zJ′) spin interactions, yielding J1 = –156(4) cm–1, J2 = –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.

AB - With maleate, [Cu5(ahpha)4]2+ gives two complexes, [Cu5(ahpha)4(DMF)2](MalH)2·2DMF (1) and [Cu5(ahpha)4(MalH)2] (2) (ahpha2– is 3-amino-3-hydroximinopropane hydroxamate; MalH2 is maleic acid). Both 1 and 2 contain non-oligomerized [Cu5(ahpha)4]2+ metallacrown blocks; in 1, two MalH– are bound to [Cu5(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 |ΔMs| = 1 and |ΔMs| = 2 resonances around 3200 G (g ≈ 2.19) and 1600 G (g ≈ 4.25) were observed for the Cu5 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 χMT vs. T model using a spin Hamiltonian accounting for central–peripheral (J1), peripheral–peripheral (J2) Cu2+–Cu2+ and intercrown (zJ′) spin interactions, yielding J1 = –156(4) cm–1, J2 = –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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DO - 10.1002/ejic.201700976

M3 - Article

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VL - 2017

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EP - 4878

JO - Berichte der deutschen chemischen Gesellschaft

JF - Berichte der deutschen chemischen Gesellschaft

SN - 0365-9496

IS - 41

ER -

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

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