Synthesis and crystal structures of lanthanide 4-benzyloxy benzoates: Influence of electron-withdrawing and electron-donating groups on luminescent properties

Abstract

Three new 4-benzyloxy benzoic acid derivatives [4-benzyloxy benzoic acid = HL1; 3-methoxy-4-benzyloxy benzoic acid = HL2; 3-nitro-4-benzyloxy benzoic acid = HL3] have been employed as ligands for the support of six lanthanide coordination compounds [Tb³⁺ = 1–3; Eu³⁺ = 4–6] with the aim of testing the influence of electron releasing (-OMe) or electron withdrawing (-NO₂) substituents on the photophysical properties. The new complexes have been characterized by a variety of spectroscopic techniques and two of the Tb³⁺ complexes [1 and 2] have been structurally authenticated by single-crystal X-ray diffraction. Compounds 1 and 2 crystallize in the monoclinic space group P2₁/n and their molecular structures consist of homodinuclear species that are bridged by two oxygen atoms from two benzoate ligands. In the case of 1, the carboxylate ligands coordinate to the central Tb³⁺ ion in bidentate chelating and bidentate bridging modes. By contrast, three different coordination modes (bidentate chelating, bidentate bridging and monodentate) are observed in the case of compound 2. Examination of the packing diagrams for 1 and 2 revealed the presence of a one-dimensional molecular array that is held together by intermolecular hydrogen-bonding interactions. The incorporation of an electron-releasing substituent on position 3 of 4-benzyloxy benzoic acid increases the electron density of the ligand and consequently improves the photoluminescence of the Tb³⁺ complexes. On the other hand, the presence of an electron-withdrawing group at this position dramatically decreases the overall sensitization efficiency of the Tb³⁺-centered luminescence due to dissipation of the excitation energy by means of a π*-n transition of the NO₂ substituent along with the participation of the ILCT bands. The weaker photoluminescence of the Eu³⁺ complexes is attributable to the poor match of the triplet energy levels of the 4-benzyloxy benzoic acid derivatives with that of the emitting level of the central metal ion.