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Title: Optimizing the Electronic Properties of Photoactive Anticancer Oxypyridine-Bridged Dirhodium(II,II) Complexes

A series of partial paddlewheel dirhodium compounds of general formula cis-[Rh 2(xhp) 2(CH 3CN) n][BF 4] 2 (n = 5 or 6) were synthesized {xhp = 6-R-2-oxypyridine ligands, R = -CH 3 (mhp), -F (fhp), -Cl (chp)}. X-ray crystallographic studies indicate the aforementioned compounds contain two cis-oriented bridging xhp ligands, with the remaining sites being coordinated by CH 3CN ligands. The lability of the equatorial (eq) CH 3CN groups in these complexes in solution is in the order -CH 3 > -Cl > -F, in accord with the more electron rich bridging ligands exerting a stronger trans effect. In the case of cis-[Rh 2(chp) 2(CH 3CN) 6][BF 4] 2 (5), light irradiation enhances the production of the aqua adducts in which eq CH 3CN is replaced by H 2O molecules, whereas the formation of the aqua species for cis-[Rh 2(fhp) 2(CH 3CN) 6][BF 4] 2 (7) is only slightly increased by irradiation. The potential of both compounds to act as photochemotherapy agents was evaluated. A 16.4-fold increase in cytotoxicity against the HeLa cell line was observed for 5 upon 30 min irradiation (λ > 400 nm), in contrast to the nontoxic compound 7, which is in accord with the resultsmore » from the photochemistry. Furthermore, the cell death mechanism induced by 5 was determined to be apoptosis. In conclusion, these results clearly demonstrate the importance of tuning the ligand field around the dimetal center to maximize the photoreactivity and achieve the best photodynamic action.« less
Authors:
 [1] ;  [1] ;  [2] ;  [3] ;  [2] ;  [1]
  1. Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry
  2. The Ohio State Univ., Columbus, OH (United States). Dept. of Chemistry and Biochemistry
  3. Texas A & M Univ., College Station, TX (United States). Dept. of Biochemistry and Biophysics
Publication Date:
Grant/Contract Number:
SC0010542; CHE-0541587
Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 136; Journal Issue: 49; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
The Ohio State Univ., Columbus, OH (United States); Texas A & M Univ., College Station, TX (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Welch Foundation, Houston, TX (United States); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 62 RADIOLOGY AND NUCLEAR MEDICINE; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
OSTI Identifier:
1430198

Li, Zhanyong, David, Amanda, Albani, Bryan A., Pellois, Jean-Philippe, Turro, Claudia, and Dunbar, Kim R.. Optimizing the Electronic Properties of Photoactive Anticancer Oxypyridine-Bridged Dirhodium(II,II) Complexes. United States: N. p., Web. doi:10.1021/ja5078359.
Li, Zhanyong, David, Amanda, Albani, Bryan A., Pellois, Jean-Philippe, Turro, Claudia, & Dunbar, Kim R.. Optimizing the Electronic Properties of Photoactive Anticancer Oxypyridine-Bridged Dirhodium(II,II) Complexes. United States. doi:10.1021/ja5078359.
Li, Zhanyong, David, Amanda, Albani, Bryan A., Pellois, Jean-Philippe, Turro, Claudia, and Dunbar, Kim R.. 2014. "Optimizing the Electronic Properties of Photoactive Anticancer Oxypyridine-Bridged Dirhodium(II,II) Complexes". United States. doi:10.1021/ja5078359. https://www.osti.gov/servlets/purl/1430198.
@article{osti_1430198,
title = {Optimizing the Electronic Properties of Photoactive Anticancer Oxypyridine-Bridged Dirhodium(II,II) Complexes},
author = {Li, Zhanyong and David, Amanda and Albani, Bryan A. and Pellois, Jean-Philippe and Turro, Claudia and Dunbar, Kim R.},
abstractNote = {A series of partial paddlewheel dirhodium compounds of general formula cis-[Rh2(xhp)2(CH3CN)n][BF4]2 (n = 5 or 6) were synthesized {xhp = 6-R-2-oxypyridine ligands, R = -CH3 (mhp), -F (fhp), -Cl (chp)}. X-ray crystallographic studies indicate the aforementioned compounds contain two cis-oriented bridging xhp ligands, with the remaining sites being coordinated by CH3CN ligands. The lability of the equatorial (eq) CH3CN groups in these complexes in solution is in the order -CH3 > -Cl > -F, in accord with the more electron rich bridging ligands exerting a stronger trans effect. In the case of cis-[Rh2(chp)2(CH3CN)6][BF4]2 (5), light irradiation enhances the production of the aqua adducts in which eq CH3CN is replaced by H2O molecules, whereas the formation of the aqua species for cis-[Rh2(fhp)2(CH3CN)6][BF4]2 (7) is only slightly increased by irradiation. The potential of both compounds to act as photochemotherapy agents was evaluated. A 16.4-fold increase in cytotoxicity against the HeLa cell line was observed for 5 upon 30 min irradiation (λ > 400 nm), in contrast to the nontoxic compound 7, which is in accord with the results from the photochemistry. Furthermore, the cell death mechanism induced by 5 was determined to be apoptosis. In conclusion, these results clearly demonstrate the importance of tuning the ligand field around the dimetal center to maximize the photoreactivity and achieve the best photodynamic action.},
doi = {10.1021/ja5078359},
journal = {Journal of the American Chemical Society},
number = 49,
volume = 136,
place = {United States},
year = {2014},
month = {12}
}