The heterometallic complex [Co(4)Fe(2)OSae(8)]·4DMF·H(2)O (1) was synthesized by one-pot reaction of cobalt powder with iron chloride in a dimethylformamide solution of salicylidene-2-ethanolamine (H(2)Sae) and characterized by single crystal X-ray diffraction analysis, magnetic measurements, high frequency electron paramagnetic resonance (HF-EPR), and Mössbauer spectroscopies. The exchange coupling in the Fe(III)-Fe(III) pair is of antiferromagnetic behavior with J/hc = -190 cm(-1). The HF-EPR spectra reveal an unusual pattern with a hardly detectable triplet signal of the Fe(III) dimer. The magnitude of D (ca. 13.9 cm(-1)) was found to be much larger than in related dimers. The catalytic investigations disclosed an outstanding activity of 1 toward oxidation of cycloalkanes with hydrogen peroxide, under mild conditions. The most efficient system showed a turnover number (TON) of 3.57 × 10(3) with the concomitant overall yield of 26% for cyclohexane, and 2.28 × 10(3)/46%, respectively, for cyclooctane. A remarkable turnover frequency (TOF) of 1.12 × 10(4) h(-1) (the highest initial rate W(0) = 3.5 × 10(-4) M s(-1)) was achieved in oxidation of cyclohexane. Kinetic experiments and selectivity parameters led to the conclusion that hydroxyl radicals are active (attacking C-H bonds) species. Kinetic and electrospray ionization mass spectrometry (ESI-MS) data allowed us to assume that the trinuclear heterometallic particle [Co(2)Fe(Sae)(4)](+), originated from 1 in solution, could be responsible for efficient generation of hydroxyl radicals from hydrogen peroxide.
The present study reports the synthesis, characterization, and crystal structure of a novel bioactive metal-organic framework, [Ag4(µ-PTA)2(µ3-PTA)2(µ4-pma)(H2O)2]n·6nH2O (bioMOF 1), which was assembled from silver(I) oxide, 1,3,5-triaza-7-phosphaadamantane (PTA), and pyromellitic acid (H4pma). This product was isolated as a stable microcrystalline solid and characterized by standard methods, including elemental analysis, 1H and 31P{1H} NMR and FTIR spectroscopy, and single crystal X-ray diffraction. The crystal structure of 1 disclosed a very complex ribbon-pillared 3D metal-organic framework driven by three different types of bridging ligands (µ-PTA, µ3-PTA, and µ4-pma4−). Various bioactivity characteristics of bioMOF 1 were investigated, revealing that this compound acts as a potent antimicrobial against pathogenic strains of standard Gram-negative (Escherichia coli, Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus) bacteria, as well as a yeast (Candida albicans). Further, 1 showed significant antiviral activity against human adenovirus 36 (HAdV-36). Finally, bioMOF 1 revealed high cytotoxicity toward an abnormal epithelioid cervix carcinoma (HeLa) cell line with low toxicity toward a normal human dermal fibroblast (NHDF) cell line. This study not only broadens the family of PTA-based coordination polymers but also highlights their promising multifaceted bioactivity.
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