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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
Authors:Maxim A. Shmelev  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  Igor L. Eremenko
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.
Keywords:cadmium-lanthanide(III) complexes   zinc-lanthanide(III) complexes   pentafluorobenzoic acid   coordination polymer   single crystal X-ray   magnetochemistry   photoluminescence
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