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Four ternary lanthanide(III) complexes, namely [Eu(Anpp)(TTA)3] (1), [Tb(Anpp)(TTA)3] (2), [Eu(Pypp)(TTA)3] (3) and [Tb(Pypp)(TTA)3] (4), [TTA = 1,1,1-trifluoro-3-(2-theonyl)acetone, Anpp = 3-(anthracen-9-yl)-1-(pyridine-2-yl)prop-2-en-1-one, Pypp = 3-(pyren-1-yl)-1-(pyridine-2-yl)prop-2-en-1-one] were designed, synthesized and characterized by various spectroscopic techniques like FT-IR, 1H-NMR, ESI-MS, UV-Vis and spectral emission studies. [Eu(Pypp)(TTA)3] (3) was structurally characterized, showing an eight coordinated {EuN1O7} square antiprismatic geometry with one N,O-donor chalcone and three O,O-donor β-diketonate ligands. Detailed photophysical properties like excited state lifetime (τ) and hydration number (q) were determined. The presence of three TTA ligands inhibits non-radiative deactivation with lifetimes in H2O in the range of 0.306–0.445 ms. The calculated hydration number (q) values (0.37–0.63) from the excited state lifetime measurements show the absence of any bound H2O molecules in the coordinatively saturated complexes (q < 1). Complexes 1–4 were studied for their biological interactions with DNA and protein and their DNA photocleavage activity was investigated. The binding constants with CT-DNA (Kb = 1.15–8.8 × 105 M−1) and HSA (KHSA = 6.5–8.1 × 105 M−1) of complexes 1–4 show their significant affinity towards these biological targets. Incorporation of chalcone ligands containing anthracene or pyrene as a photosensitizing moiety in these complexes were effective in generating reactive oxygen species (ROS). Complexes 1–4 display moderate photocleavage of supercoiled (SC)-DNA to its nicked circular (NC) form on exposure to UV-A light of 365 nm through the generation of singlet oxygen (1O2) and hydroxyl radicals (˙OH) under physiological conditions.

Ternary Eu(iii) and Tb(iii) β-diketonate complexes containing chalcones: photophysical studies and biological outlook