Magnetic and sorption properties of supramolecular systems based on pentanuclear copper(II) 12-metallacrown-4 complexes and isomeric phthalates: Structural modeling of the different stages of alcohol sorption

Anna V. Pavlishchuk; Sergey V. Kolotilov; Matthias Zeller; Oleksiy V. Shvets; Igor O. Fritsky; Samuel E. Lofland; Anthony W. Addison; Allen D. Hunter

doi:10.1002/ejic.201100790

Magnetic and sorption properties of supramolecular systems based on pentanuclear copper(II) 12-metallacrown-4 complexes and isomeric phthalates: Structural modeling of the different stages of alcohol sorption

Anna V. Pavlishchuk
, Sergey V. Kolotilov
, Matthias Zeller
, Oleksiy V. Shvets
, Igor O. Fritsky
, Samuel E. Lofland
, Anthony W. Addison
, Allen D. Hunter

Physics

Research output: Contribution to journal › Article › peer-review

50 Scopus citations

Abstract

Metathesis of the perchlorate anions in [Cu₅(ahpha) ₄](ClO₄)₂·4H₂O, where ahpha^2- is the dianion of 3-amino-3-hydroximinopropane hydroxamic acid, with m- and p-phthalates resulted in formation of [Cu₅(ahpha) ₄(m-C₈H₄O₄)(H₂O)] ·9H₂O (1), [Cu₅(ahpha)₄(m-C ₈H₄O₄)(H₂O)]·2MeOH· DMF (1a) and [Cu₅(ahpha)₄(p-C₈H ₄O₄)(H₂O)₂]₂· 14H₂O (2). Molecules in the structures of 1, 1a and 2 are held together by noncovalent interactions, and the lattices contain voids filled with water molecules. Compounds 1 and 1a differ in the mode of m-phthalate coordination, solvent type, and crystal lattice content. Desolvated 1 and 2 sorb gaseous MeOH and EtOH. Whereas the MeOH sorption capacity was very similar for 1 and 2 (about 0.14 cm³/g at PP_S^-1 = 0.9, where P is the current methanol pressure and P_S the saturation vapor pressure of methanol at 293 K), the capacity of 2 to sorb EtOH was about 1.5 times as high as that of 1. To a certain extent, the structures of 1 and 1a can be considered as models of compounds that can form at different stages during alcohol sorption by desolvated 1. The Ï_MT vs. T data for 1 and 2 could be fitted with a model based on the Hamiltonian H(Cu^II ₅) = -2J₁(S₁·S₂ + S ₁·S₃ + S₁·S₄ + S ₁·S₅) - 2J₂(S₂·S ₅ + S₂·S₃ + S₃·S ₄ + S₄·S₅), where S₁ represents the spins of the central Cu^II ions and S ₂-S₄ correspond to the spins of the peripheral Cu ^II ions. The best fits corresponded to J₁ = -129(3) cm^-1, J₂ = -66(1) cm^-1 and zJ′ = -2.5(2) cm^-1 at g_Cu = 2.12(1) for 1, and J₁ = -163(3) cm^-1, J₂ = -78(1) cm^-1 and zJ′ = -1.5(1) cm^-1 at g_Cu = 2.05(1) for 2. Three complexes were obtained starting from a pentacopper 12-metallacrown-4 and isomeric benzenedicarboxylates. The structures of the complexes determined by XRD may be considered as models of intermediates that form during the interaction of these non-rigid sorbents with alcohols.

Original language	English (US)
Pages (from-to)	4826-4836
Number of pages	11
Journal	European Journal of Inorganic Chemistry
Issue number	31
DOIs	https://doi.org/10.1002/ejic.201100790
State	Published - Nov 2011

All Science Journal Classification (ASJC) codes

Inorganic Chemistry

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10.1002/ejic.201100790

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Pavlishchuk, A. V., Kolotilov, S. V., Zeller, M., Shvets, O. V., Fritsky, I. O., Lofland, S. E., Addison, A. W., & Hunter, A. D. (2011). Magnetic and sorption properties of supramolecular systems based on pentanuclear copper(II) 12-metallacrown-4 complexes and isomeric phthalates: Structural modeling of the different stages of alcohol sorption. European Journal of Inorganic Chemistry, (31), 4826-4836. https://doi.org/10.1002/ejic.201100790

@article{3d3ebdac20b14e6c8cc11cf40bbdfb91,

title = "Magnetic and sorption properties of supramolecular systems based on pentanuclear copper(II) 12-metallacrown-4 complexes and isomeric phthalates: Structural modeling of the different stages of alcohol sorption",

abstract = "Metathesis of the perchlorate anions in [Cu5(ahpha) 4](ClO4)2·4H2O, where ahpha2- is the dianion of 3-amino-3-hydroximinopropane hydroxamic acid, with m- and p-phthalates resulted in formation of [Cu5(ahpha) 4(m-C8H4O4)(H2O)] ·9H2O (1), [Cu5(ahpha)4(m-C 8H4O4)(H2O)]·2MeOH· DMF (1a) and [Cu5(ahpha)4(p-C8H 4O4)(H2O)2]2· 14H2O (2). Molecules in the structures of 1, 1a and 2 are held together by noncovalent interactions, and the lattices contain voids filled with water molecules. Compounds 1 and 1a differ in the mode of m-phthalate coordination, solvent type, and crystal lattice content. Desolvated 1 and 2 sorb gaseous MeOH and EtOH. Whereas the MeOH sorption capacity was very similar for 1 and 2 (about 0.14 cm3/g at PPS-1 = 0.9, where P is the current methanol pressure and PS the saturation vapor pressure of methanol at 293 K), the capacity of 2 to sorb EtOH was about 1.5 times as high as that of 1. To a certain extent, the structures of 1 and 1a can be considered as models of compounds that can form at different stages during alcohol sorption by desolvated 1. The {\"I}MT vs. T data for 1 and 2 could be fitted with a model based on the Hamiltonian H(CuII 5) = -2J1(S1·S2 + S 1·S3 + S1·S4 + S 1·S5) - 2J2(S2·S 5 + S2·S3 + S3·S 4 + S4·S5), where S1 represents the spins of the central CuII ions and S 2-S4 correspond to the spins of the peripheral Cu II ions. The best fits corresponded to J1 = -129(3) cm-1, J2 = -66(1) cm-1 and zJ′ = -2.5(2) cm-1 at gCu = 2.12(1) for 1, and J1 = -163(3) cm-1, J2 = -78(1) cm-1 and zJ′ = -1.5(1) cm-1 at gCu = 2.05(1) for 2. Three complexes were obtained starting from a pentacopper 12-metallacrown-4 and isomeric benzenedicarboxylates. The structures of the complexes determined by XRD may be considered as models of intermediates that form during the interaction of these non-rigid sorbents with alcohols.",

author = "Pavlishchuk, \{Anna V.\} and Kolotilov, \{Sergey V.\} and Matthias Zeller and Shvets, \{Oleksiy V.\} and Fritsky, \{Igor O.\} and Lofland, \{Samuel E.\} and Addison, \{Anthony W.\} and Hunter, \{Allen D.\}",

year = "2011",

month = nov,

doi = "10.1002/ejic.201100790",

language = "English (US)",

pages = "4826--4836",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

number = "31",

}

Pavlishchuk, AV, Kolotilov, SV, Zeller, M, Shvets, OV, Fritsky, IO, Lofland, SE, Addison, AW & Hunter, AD 2011, 'Magnetic and sorption properties of supramolecular systems based on pentanuclear copper(II) 12-metallacrown-4 complexes and isomeric phthalates: Structural modeling of the different stages of alcohol sorption', European Journal of Inorganic Chemistry, no. 31, pp. 4826-4836. https://doi.org/10.1002/ejic.201100790

Magnetic and sorption properties of supramolecular systems based on pentanuclear copper(II) 12-metallacrown-4 complexes and isomeric phthalates: Structural modeling of the different stages of alcohol sorption. / Pavlishchuk, Anna V.; Kolotilov, Sergey V.; Zeller, Matthias et al.
In: European Journal of Inorganic Chemistry, No. 31, 11.2011, p. 4826-4836.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Magnetic and sorption properties of supramolecular systems based on pentanuclear copper(II) 12-metallacrown-4 complexes and isomeric phthalates

T2 - Structural modeling of the different stages of alcohol sorption

AU - Pavlishchuk, Anna V.

AU - Kolotilov, Sergey V.

AU - Zeller, Matthias

AU - Shvets, Oleksiy V.

AU - Fritsky, Igor O.

AU - Lofland, Samuel E.

AU - Addison, Anthony W.

AU - Hunter, Allen D.

PY - 2011/11

Y1 - 2011/11

N2 - Metathesis of the perchlorate anions in [Cu5(ahpha) 4](ClO4)2·4H2O, where ahpha2- is the dianion of 3-amino-3-hydroximinopropane hydroxamic acid, with m- and p-phthalates resulted in formation of [Cu5(ahpha) 4(m-C8H4O4)(H2O)] ·9H2O (1), [Cu5(ahpha)4(m-C 8H4O4)(H2O)]·2MeOH· DMF (1a) and [Cu5(ahpha)4(p-C8H 4O4)(H2O)2]2· 14H2O (2). Molecules in the structures of 1, 1a and 2 are held together by noncovalent interactions, and the lattices contain voids filled with water molecules. Compounds 1 and 1a differ in the mode of m-phthalate coordination, solvent type, and crystal lattice content. Desolvated 1 and 2 sorb gaseous MeOH and EtOH. Whereas the MeOH sorption capacity was very similar for 1 and 2 (about 0.14 cm3/g at PPS-1 = 0.9, where P is the current methanol pressure and PS the saturation vapor pressure of methanol at 293 K), the capacity of 2 to sorb EtOH was about 1.5 times as high as that of 1. To a certain extent, the structures of 1 and 1a can be considered as models of compounds that can form at different stages during alcohol sorption by desolvated 1. The ÏMT vs. T data for 1 and 2 could be fitted with a model based on the Hamiltonian H(CuII 5) = -2J1(S1·S2 + S 1·S3 + S1·S4 + S 1·S5) - 2J2(S2·S 5 + S2·S3 + S3·S 4 + S4·S5), where S1 represents the spins of the central CuII ions and S 2-S4 correspond to the spins of the peripheral Cu II ions. The best fits corresponded to J1 = -129(3) cm-1, J2 = -66(1) cm-1 and zJ′ = -2.5(2) cm-1 at gCu = 2.12(1) for 1, and J1 = -163(3) cm-1, J2 = -78(1) cm-1 and zJ′ = -1.5(1) cm-1 at gCu = 2.05(1) for 2. Three complexes were obtained starting from a pentacopper 12-metallacrown-4 and isomeric benzenedicarboxylates. The structures of the complexes determined by XRD may be considered as models of intermediates that form during the interaction of these non-rigid sorbents with alcohols.

AB - Metathesis of the perchlorate anions in [Cu5(ahpha) 4](ClO4)2·4H2O, where ahpha2- is the dianion of 3-amino-3-hydroximinopropane hydroxamic acid, with m- and p-phthalates resulted in formation of [Cu5(ahpha) 4(m-C8H4O4)(H2O)] ·9H2O (1), [Cu5(ahpha)4(m-C 8H4O4)(H2O)]·2MeOH· DMF (1a) and [Cu5(ahpha)4(p-C8H 4O4)(H2O)2]2· 14H2O (2). Molecules in the structures of 1, 1a and 2 are held together by noncovalent interactions, and the lattices contain voids filled with water molecules. Compounds 1 and 1a differ in the mode of m-phthalate coordination, solvent type, and crystal lattice content. Desolvated 1 and 2 sorb gaseous MeOH and EtOH. Whereas the MeOH sorption capacity was very similar for 1 and 2 (about 0.14 cm3/g at PPS-1 = 0.9, where P is the current methanol pressure and PS the saturation vapor pressure of methanol at 293 K), the capacity of 2 to sorb EtOH was about 1.5 times as high as that of 1. To a certain extent, the structures of 1 and 1a can be considered as models of compounds that can form at different stages during alcohol sorption by desolvated 1. The ÏMT vs. T data for 1 and 2 could be fitted with a model based on the Hamiltonian H(CuII 5) = -2J1(S1·S2 + S 1·S3 + S1·S4 + S 1·S5) - 2J2(S2·S 5 + S2·S3 + S3·S 4 + S4·S5), where S1 represents the spins of the central CuII ions and S 2-S4 correspond to the spins of the peripheral Cu II ions. The best fits corresponded to J1 = -129(3) cm-1, J2 = -66(1) cm-1 and zJ′ = -2.5(2) cm-1 at gCu = 2.12(1) for 1, and J1 = -163(3) cm-1, J2 = -78(1) cm-1 and zJ′ = -1.5(1) cm-1 at gCu = 2.05(1) for 2. Three complexes were obtained starting from a pentacopper 12-metallacrown-4 and isomeric benzenedicarboxylates. The structures of the complexes determined by XRD may be considered as models of intermediates that form during the interaction of these non-rigid sorbents with alcohols.

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U2 - 10.1002/ejic.201100790

DO - 10.1002/ejic.201100790

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JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

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Pavlishchuk AV, Kolotilov SV, Zeller M, Shvets OV, Fritsky IO, Lofland SE et al. Magnetic and sorption properties of supramolecular systems based on pentanuclear copper(II) 12-metallacrown-4 complexes and isomeric phthalates: Structural modeling of the different stages of alcohol sorption. European Journal of Inorganic Chemistry. 2011 Nov;(31):4826-4836. doi: 10.1002/ejic.201100790

Magnetic and sorption properties of supramolecular systems based on pentanuclear copper(II) 12-metallacrown-4 complexes and isomeric phthalates: Structural modeling of the different stages of alcohol sorption

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