Synthesis, Structure, and Photoluminescent Properties of Zn2+, Mn2+, Cd2+, Eu3+, and Tb3+ Complexes with 4-Allyl-2,3,5,6-Tetrafluorobenzoic Acid Anions and 1,10-Phenanthroline

We report a synthesis of a series of molecular compounds and coordination polymers of Zn2+, Mn2+ Cd2+, Eu3+, and Tb3+ with 4-allyl-2,3,5,6-tetrafluorobenzoic acid (4-Afb) anions and 1,10-phenanthroline with compositions [Zn(H2O)(phen)(4-Afb)(2)] (1), [Mn(H2O)(phen)(4-Afb)(2)](n)<middle dot>nH(2)O (2), [Cd(H2O)(phen)(4-Afb)(2)](n) (3), [Cd(phen)(4-Afb)(2)](n) (4), [Ln(2)(phen)(2)(4-Afb)(6)] (Ln = Eu 5Eu; Tb 5Tb). It is shown that the obtained cadmium coordination polymers have various compositions and structures, depending on crystallization conditions. The prepared compounds are characterized by single-crystal XRD, powder XRD, IR spectroscopy, and CHN analysis. Noncovalent interactions are analyzed using the Hirshfeld surface analysis. It is determined that the crystal packings is mainly stabilized by pi & ctdot;pi, C-H & ctdot;F, and C-F & ctdot;pi interactions. The photoluminescent properties of the 5Eu and 5Tb complexes are studied. It is shown that the structure-forming effects of non-covalent "arene-perfluoroarene" interactions can be possibly used for preorganizing reactive functional groups in the crystal.