Studies on the reactions of 3,2′-polymethylene-2-phenylbenzo[b]-1,10-phenanthrolines with Ru(tpy)Cl3 and properties of the products

Abstract

A series of 3,2-polymethylene-2-phenylbenzo[b]-1,10-phenanthrolines was reacted with Ru(tpy)Cl to afford two ruthenium (Ru) complexes, a pentaaza-coordinated (N5Cl) complex [Ru(tpy)(L)Cl] and a hexa-coordinated (N5C) complex [Ru(tpy)(L)]. The ratio of these two complexes was found to be highly dependent on the length of the polymethylene bridge between terminal phenyl and central pyridine rings. The reaction between the dimethylene-bridged ligand and Ru(tpy)Cl afforded a hexa-coordinated (N5C) complex as an only isolatable product in 83% yield, while the others afforded pentaaza-coordinated products and hexa-coordinated products in ratios of 1:1.6-3.5 with 80-90% overall yields. The UV spectra of pentaaza-coordinated complexes (N5Cl) and hexa-coordinated (N5C) cycloruthenated complexes were similar to show absorbances at 253-255, 276-286, 312-324, 360-373, and 490-532 nm. All of these complexes showed greenish blue light emissions in the range 450-460 nm upon excitation in the range 368-382 nm, while excitation at 500-532 nm resulted in green light emissions at 570 nm for pentaaza-coordinated complexes and 577-579 nm for hexaaza-coordinated species. Irradiation of the plasmid (100 μM) in the presence of 8c (λ > 395 nm, 10 min) in air resulted in single-strand cleavage leading to the production of nicked plasmid (Form II), probably via intercalation.

Investigation of the Relationship between Electronic Structures and Bioactivities of Polypyridyl Ru(II) Complexes

“…The PL spectrums were recorded by Hitachi fluorescence spectrophotometer F-7100. The synthetic procedure was according to the literature in previous work [39][40][41]. A mixture of R-phen (0.5 mmol), Ru(tpy)Cl 3 (220 mg, 0.5 mmol), and LiCl (105.4 mg 2.5 mmol) in EtOH: H 2 O (3:1, 50 mL) with Et 3 N (3 drops) was refluxed for 12 h. After that, the dark red reaction mixture was cooled to room temperature, then concentrated in vacuo.…”

Increasing the cytotoxicity of Ru(ii) polypyridyl complexes by tuning the electron-donating ability of 1,10-phenanthroline ligands

“…[6][7][8][9][10][11][12][13] Preclinical and clinical research showed that ruthenium (Ru) complexes could be alternatives to replace platinum drugs due to their advantages of low systemic toxicities and high efficacies in treating cancer patients. [14][15][16][17] In fact, promising Ru complexes, NKP-1019/IT-139 and NAMI-A, are in clinical trials as chemotherapeutic agents. Moreover, a polypyridyl complex, TLD-1433 as a photosensitizer is in phase II clinical trial for photodynamic therapy against bladder cancer.…”