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Varying the temperature of the reaction of [{Cd(pfb)(H 2 O) 4 } +   n  · n (pfb) − ], [Ln 2 (pfb) 6 (H 2 O) 8 ]·H 2 O (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   · 1.5 n MeCN (Ln = Eu (I), Gd (II), Tb (III), Dy (IV)) which were isolated at 25 °C, and molecular compounds [Tb 2 Cd 2 (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 Ln 2 Cd 2  fragments. Replacement of cadmium with zinc in the reaction resulted in molecular compounds Ln 2 Zn 2  [Ln 2 Zn 2 (pfb) 10 (phen) 2 ]·4MeCN (Ln = Eu (VI), Tb (VIII), Dy (IX)) and [Gd 2 Zn 2 (pfb) 10 (H 2 O) 2 (phen) 2 ]·4MeCN (VII). A new molecular EuCd complex [Eu 2 Cd 2 (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.

materials

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