期刊
INORGANICA CHIMICA ACTA
卷 560, 期 -, 页码 -出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2023.121831
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Three BODIPY-Ru(II) complexes were synthesized by coordinating [Ru(bpy)2Cl]+ complexes to BODIPY ligands. The spectroscopic and electrochemical properties of the complexes were characterized. The complexes exhibited intense absorption peaks due to the pi pi* transitions localized on the BODIPY core, and additional charge transfer transitions associated with the metal center. The complexes showed significant singlet oxygen generation and were able to induce photo-nicking of DNA.
Three BODIPY dyes with 4-phenylpyridyl or 4-pyridyl meso-substituents have been synthesized and characterized. Coordination [Ru(bpy)2Cl]+ complexes to the pyridyl N-atoms has resulted in a series of BODIPY-Ru(II) complexes, Ru-1, Ru-2, and Ru-3. The spectroscopic and electrochemical properties of the BODIPY dyes and their Ru(II) analogs have been characterized. The electronic spectra of the dyes and dye-complexes reveal the intense absorption typical of the (pi pi*) transitions localized on the BODIPY core. The extended aromatic groups of dye 3 and its analog Ru-3 exhibit a 100 nm bathochromic shift in the BODIPY (pi pi*) transition. Additional metal-centered charge transfer transitions associated with the [Ru(bpy)2Cl]+ moieties are observed at higher energy compared to the BODIPY transitions. Extended DFT calculations of dyes 1 and 2 and their Ru(II) analogues Ru-1 and Ru-2 are in agreement to the experimental data. All three of the BODIPY-Ru(II) complexes exhibit significant singlet oxygen generation determined by the use of a singlet oxygen trap in acetonitrile solutions. Photo-reactions of the complexes in buffered aqueous solutions containing circular plasmid DNA (cpDNA) indicate that complexes Ru-1 and Ru-2 convert the cpDNA to its nicked form within minutes of irradiation. The Ru-3 complexes generates enough singlet oxygen to begin the photo-nicking of cpDNA but complete nicking of all cpDNA was not observed. This is most likely due to light induced decomposition of Ru-3 to its constituents; thereby, preventing further generation of singlet oxygen.
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