与五氟苯甲酸根阴离子形成的分子和聚合物LnM（Ln = Eu、Gd、Tb、Dy；M = Zn、Cd）配合物：温度和堆积效应在结构中的作用；磁性和发光性质

Molecular and Polymer LnM (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.

作者信息

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

机构信息

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.

出版信息

Materials (Basel). 2020 Dec 13;13(24):5689. doi: 10.3390/ma13245689.

Varying the temperature of the reaction of [{Cd(pfb)(HO)}·(pfb)], [Ln(pfb)(HO)]·HO (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)(phen)]1.5MeCN (Ln = Eu (I), Gd (II), Tb (III), Dy (IV)) which were isolated at 25 °C, and molecular compounds [TbCd(pfb)(phen)] (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 LnCd fragments. Replacement of cadmium with zinc in the reaction resulted in molecular compounds LnZn [LnZn(pfb)(phen)]·4MeCN (Ln = Eu (VI), Tb (VIII), Dy (IX)) and [GdZn(pfb)(HO)(phen)]·4MeCN (VII). A new molecular EuCd complex [EuCd(pfb)(phen)]·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.

在乙腈中改变[{Cd(pfb)(HO)}·(pfb)]、[Ln(pfb)(HO)]·HO（Hpfb = 五氟苯甲酸）和1,10 - 菲咯啉（phen）的反应温度，然后进行结晶，得到了两种类型的产物：在25°C下分离得到的一维聚合物[LnCd(pfb)(phen)]1.5MeCN（Ln = Eu (I)、Gd (II)、Tb (III)、Dy (IV)），以及在75°C下形成的分子化合物[TbCd(pfb)(phen)]（V）。由于相邻四核LnCd片段中phen和pfb的芳环之间的分子内和分子间相互作用，从分子结构向聚合物结构的转变成为可能。在反应中用锌取代镉，得到分子化合物LnZn [LnZn(pfb)(phen)]·4MeCN（Ln = Eu (VI)、Tb (VIII)、Dy (IX)）和[GdZn(pfb)(HO)(phen)]·4MeCN（VII）。从五氟苯甲酸镉、锌和铕的混合物中分离出一种新的分子铕镉配合物[EuCd(pfb)(phen)]·4MeCN（X）。配合物II - IV、VII和IX在液氦温度下于非零磁场中表现出磁弛豫。发光研究揭示了含有铕(III)和铽(III)离子的配合物发出明亮的光。