Mono- and poly-nuclear copper(II) carboxylates with flourous ligands: Synthesis, structure and improved properties.

• Synthesis of mononuclear and poly-nuclear copper(II) complexes. • Characterization through FT–IR, UV–Visible, ESR, electrochemical and powder and single crystal XRD techniques. • Structural description. • DNA-binding, antibacterial studies and DFT studies. Polynuclear copper(II) complexes [Cu(para -fluorophenyl acetate) 2 n (1) and [Cu(para -nitrophenyl acetate) 2 n (2) were converted in-situ to mono-nuclear complexes [Cu(para -fluorophenyl acetate) 2 (1,10-Phenanthroline)(H 2 O)] (3) and [Cu(para -nitrophenyl acetate) 2 (2,2́-Bipyridine)(H 2 O)].3H 2 O (4). The complexes were isolated in quantitative yield, purified and characterized using FT-IR, absorption, electrochemical, electron paramagnetic resonance and powder XRD techniques yielding results in accordance with structural data. Structures of 1 and 2 consist of directly interlinked paddlewheel units with square pyramidal geometry while those of 3 and 4 are mononuclear with octahedral and square pyramidal geometry around Cu. Fluorinated complexes 1 and 3 were found to consist of extensive intermolecular interactions while 2 and 4 contained no such interactions. Their optical band gap was around 1.4 eV which indicates semiconducting property of the complexes. Moreover, the flourous complex 3 was found to possess significant activity against Bacillus subtilis and Escherichia coli and good activity against Micrococcus luteus. A similar trend was observed in their DNA-binding potency studied through absorption as well as electrochemical solution studies yielding K b values 1.494 × 104, 1.342 × 104 and 1.411 × 104 M−1 and 7.547 × 104, 2.457 × 104 and 3.667 × 104 M−1 for 1–3, respectively. The electronic structures of the complexes elucidated using density functional theory ab -initio calculations confirmed the Intermediate states which play important role in the enhancement of the optoelectronic properties. The structure and properties of the flourous complexes were found different than their non-flourous analogues which was attributable to fluorine. [ABSTRACT FROM AUTHOR]