Molecular and Polymer Ln2M2 (Ln = Eu, Gd, Tb, Dy; M = Zn, Cd) Complexes with Pentafluorobenzoate Anions: The Role of Temperature and Stacking Effects in the Structure; Magnetic and Luminescent Properties

Shmelev, Maxim A.; Kiskin, Mikhail A.; Voronina, Julia K.; Babeshkin, Konstantin A.; Efimov, Nikolay N.; Varaksina, Evgenia A.; Korshunov, Vladislav M.; Taydakov, Ilya V.; Gogoleva, Natalia V.; Sidorov, Alexey A.; Eremenko, Igor L.

doi:10.3390/ma13245689

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Molecular and Polymer Ln₂M₂ (Ln = Eu, Gd, Tb, Dy; M = Zn, Cd) Complexes with Pentafluorobenzoate Anions: The Role of Temperature and Stacking Effects in the Structure; Magnetic and Luminescent Properties

Maxim A. Shmelev

Mikhail A. Kiskin

^1,*

Julia K. Voronina

Konstantin A. Babeshkin

Nikolay N. Efimov

Evgenia A. Varaksina

²,

Vladislav M. Korshunov

^2,3,

^2,4,

¹,

¹ and

N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russia

P. N. Lebedev Physical Institute, Russian Academy of Sciences, 119991 Moscow, Russia

Faculty of Fundamental Sciences, Bauman Moscow State Technical University, 105005 Moscow, Russia

⁴

Academic Department of Innovational Materials and Technologies Chemistry, Plekhanov Russian University of Economics, 117997 Moscow, Russia

Author to whom correspondence should be addressed.

Materials 2020, 13(24), 5689; https://doi.org/10.3390/ma13245689

Received: 12 November 2020 / Revised: 7 December 2020 / Accepted: 8 December 2020 / Published: 13 December 2020

(This article belongs to the Special Issue Coordination Polymers: Synthesis, Crystal Structure and Multifunctional Applications)

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Abstract

Varying the temperature of the reaction of [{Cd(pfb)(H₂O)₄}⁺_n·n(pfb)⁻], [Ln₂(pfb)₆(H₂O)₈]·H₂O (Hpfb = pentafluorobenzoic acid), and 1,10-phenanthroline (phen) in MeCN followed by crystallization resulted in the isolation of two type of products: 1D-polymers [LnCd(pfb)₅(phen)]_n·1.5nMeCN (Ln = Eu (I), Gd (II), Tb (III), Dy (IV)) which were isolated at 25 °C, and molecular compounds [Tb₂Cd₂(pfb)₁₀(phen)₂] (V) formed at 75 °C. The transition from a molecular to a polymer structure becomes possible because of intra- and intermolecular interactions between the aromatic cycles of phen and pfb from neighboring tetranuclear Ln₂Cd₂ fragments. Replacement of cadmium with zinc in the reaction resulted in molecular compounds Ln₂Zn₂ [Ln₂Zn₂(pfb)₁₀(phen)₂]·4MeCN (Ln = Eu (VI), Tb (VIII), Dy (IX)) and [Gd₂Zn₂(pfb)₁₀(H₂O)₂(phen)₂]·4MeCN (VII). A new molecular EuCd complex [Eu₂Cd₂(pfb)₁₀(phen)₄]·4MeCN (X)] was isolated from a mixture of cadmium, zinc, and europium pentafluorobenzoates (Cd:Zn:Ln = 1:1:2). Complexes II-IV, VII and IX exhibit magnetic relaxation at liquid helium temperatures in nonzero magnetic fields. Luminescent studies revealed a bright luminescence of complexes with europium(III) and terbium(III) ions. View Full-Text

Keywords: cadmium-lanthanide(III) complexes; zinc-lanthanide(III) complexes; pentafluorobenzoic acid; coordination polymer; single crystal X-ray; magnetochemistry; photoluminescence

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Shmelev, M.A.; Kiskin, M.A.; Voronina, J.K.; Babeshkin, K.A.; Efimov, N.N.; Varaksina, E.A.; Korshunov, V.M.; Taydakov, I.V.; Gogoleva, N.V.; Sidorov, A.A.; Eremenko, I.L. Molecular and Polymer Ln₂M₂ (Ln = Eu, Gd, Tb, Dy; M = Zn, Cd) Complexes with Pentafluorobenzoate Anions: The Role of Temperature and Stacking Effects in the Structure; Magnetic and Luminescent Properties. Materials 2020, 13, 5689. https://doi.org/10.3390/ma13245689

AMA Style

Shmelev MA, Kiskin MA, Voronina JK, Babeshkin KA, Efimov NN, Varaksina EA, Korshunov VM, Taydakov IV, Gogoleva NV, Sidorov AA, Eremenko IL. Molecular and Polymer Ln₂M₂ (Ln = Eu, Gd, Tb, Dy; M = Zn, Cd) Complexes with Pentafluorobenzoate Anions: The Role of Temperature and Stacking Effects in the Structure; Magnetic and Luminescent Properties. Materials. 2020; 13(24):5689. https://doi.org/10.3390/ma13245689

Chicago/Turabian Style

Shmelev, Maxim A., Mikhail A. Kiskin, Julia K. Voronina, Konstantin A. Babeshkin, Nikolay N. Efimov, Evgenia A. Varaksina, Vladislav M. Korshunov, Ilya V. Taydakov, Natalia V. Gogoleva, Alexey A. Sidorov, and Igor L. Eremenko. 2020. "Molecular and Polymer Ln₂M₂ (Ln = Eu, Gd, Tb, Dy; M = Zn, Cd) Complexes with Pentafluorobenzoate Anions: The Role of Temperature and Stacking Effects in the Structure; Magnetic and Luminescent Properties" Materials 13, no. 24: 5689. https://doi.org/10.3390/ma13245689

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Molecular and Polymer Ln₂M₂ (Ln = Eu, Gd, Tb, Dy; M = Zn, Cd) Complexes with Pentafluorobenzoate Anions: The Role of Temperature and Stacking Effects in the Structure; Magnetic and Luminescent Properties

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