A series of trans-pyridyl porphyrins, 5,15-di(pentafluorophenyl)-10,20-bis(2ꞌ/3ꞌ/4ꞌ-pyridyl)porphyrin (1−3), trans-dicationic pyridinium porphyrins, 5,15-di(pentafluorophenyl)-10,20-bis(2ꞌ/3ꞌ/4ꞌ-Nmethylpyridyl)porphyrins (4−6) and their copper(II) and zinc(II) derivatives were synthesized. These compounds were characterized using various spectroscopic methods, electrochemical and single crystal X-ray crystallographic studies. The trans-dicationic porphyrin derivatives exhibit red shifted absorption spectra over the simple pyridyl porphyrins. The reduction potentials of trans-pyridyl porphyrins are more positive than those of MTPPs. Crystal structure of 3c is forming networks of molecules through Zn-N coordination displaying large number of channels. The intermolecular interactions involving fluorine contributes considerably to the crystal packing in all the structures which was further confirmed by computational Hirshfeld surface analysis. The dicationic porphyrins were further explored for its DNA interaction abilities and antimicrobial activities. The UV-visible and fluorescence spectroscopic titrations indicate that the porphyrins bind with the calf thymus DNA by outside groove binding mode with or without self-stacking. The intrinsic binding constants K b of these dicationic porphyrins to DNA was found to be in the range of 10 5 −10 6 M −1 . The results reveal that among the three sets of porphyrins (4−6), the 3-/4-pyridyl derivatives display higher DNA binding activities compared to the 2-pyridyl analogues.The photocleavage experiments disclose that the porphyrins employ 1 O 2 -mediated mechanism in cleaving DNA and the freebase and zinc(II) derivatives show better photoinduced cleavage ability compared to its copper(II) analogues. The dicationic porphyrins also show significant antimicrobial activities than those of non-fluorinated analogues.Trans-dicationic pyridinium porphyrins: Synthesis, structure, electrochemical, DNA interaction and antimicrobial studies of fluorinated trans-pyridyl and trans-dicationic pyridinium porphyrins are reported and the studies indicate that they are superior artificial nucleases than its non-fluorinated analogues; bind with the calf thymus DNA by outside groove binding mode with or without self-stacking, also show significant antimicrobial activities than those of nonfluorinated analogues.
Herein, we experimentally demonstrate the enhanced nonlinear optical (NLO) response of 5,15-di(pentafluorophenyl)-10,20-bis(4-N-methylpyridyl)Zn(II) porphyrin, abbreviated as ZnP+, by utilizing Tamm plasmon polaritons formed at the interface between a truncated all-polymeric Bragg...
A2B2 porphyrin bearing 2/3‐thienyl and 2‐pyridyl moieties (P1a, P3a) and its dicationic derivatives (P2a, P4a) were synthesized in reasonably good yield. The corresponding Copper (II) (P1‐4 b) and Zinc (II) metallated (P1‐4 c) analogs were obtained by conventional methods. The synthesized compounds were characterized by various spectroscopic techniques, electrochemical studies and thermogravimetric analysis. The Copper (II) porphyrin, P1b is structurally characterized by single‐crystal X‐ray structure analysis. The ground state electronic structure and geometry optimizations are carried out by DFT calculations. The computed TD‐DFT results validate the observed optical bands and spectral features. DNA interaction studies of trans‐dicationic porphyrins were performed using spectroscopic titrations, docking studies, and gel electrophoresis experiments. All porphyrins interact with the calf thymus DNA by outside groove binding mode with self‐stacking, and the highest intrinsic binding constant of 1.29 ± 0.14×106 M‐1 is observed for P4a. Molecular docking studies reveal that the binding energy of porphyrins with DNA is around −10 kcal/mol. The antimicrobial properties of the dicationic derivatives (P2,4 a, b, c) were investigated against E. Coli and S. aureus under light and dark conditions, and the growth inhibitory effect is found to be negligible when unilluminated.
Condensation of 3‐pyridine carboxaldehyde with 2/3‐thienyl dipyrromethanes in presence of acid catalyst gives 5‐(3′‐pyridyl)‐10,15,20‐tri(2/3‐thienyl)porphyrins (S1a and S2a) due to scrambling along with the expected trans‐porphyrins. The corresponding copper(II) and zinc(II) porphyrins were also synthesized. Moreover, to study their biological properties their cationic derivatives were obtained. All the complexes were characterized by UV‐Vis, fluorescence, NMR spectroscopy, mass spectrometry and cyclic voltammetry. The cationic porphyrins bind with DNA non‐intercalatively; show singlet oxygen mediated photocleavage; phototoxic to A549 lung cancer cells through apoptotic pathway.
A new series of mono-/di-aminated meso-tetraarylporphyrins has been synthesized and characterized by conventional spectroscopic methods. Crystal structure analysis shows that interactions involving halogens are the major contributors, and the relative contributions are 56% and 53% respectively for MB2c and MB3c. All the compounds were electrochemically analyzed under different reaction conditions and showed a positive shift in the reduction and oxidation potentials. The HOMO–LUMO energy gap was altered with respect to the nature of the supporting electrolyte and reference electrodes used. The linear behavior of Randles-Sevcik plots indicate that the redox processes are diffusion controlled; the first reduction/oxidation is a reversible one-electron step whereas the second reduction/oxidation is a quasi-reversible one-electron process. Results also reveal that the mono-aminated porphyrins are more electron deficient than non-aminated and di-aminated porphyrins.
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