Design Aspects for the Development of Mixed-Metal Supramolecular Complexes Capable of Visible Light Induced Photocleavage of DNA

2003/12/09 by Alvin A. Holder, Shawn Swavey, Karen J. Brewer · 9 citations
Medicine · Biochemistry, Genetics and Molecular Biology · Chemistry · #Metal complexes synthesis and properties #DNA and Nucleic Acid Chemistry #Click Chemistry and Applications

paper · doi:10.1021/ic035029t

Abstract

Mixed-metal supramolecular complexes that couple ruthenium or osmium based light absorbers to a central rhodium(III) core have been designed which photocleave DNA upon irradiation with visible light. The complexes [[(bpy)(2)Ru(dpp)](2)RhCl(2)](PF(6))(5), [[(bpy)(2)Os(dpp)](2)RhCl(2)](PF(6))(5), and [[(tpy)RuCl(dpp)](2)RhCl(2)](PF(6))(3), where bpy = 2,2'-bipyridine, tpy = 2,2':6',2' '-terpyridine, and dpp = 2,3-bis(2-pyridyl)pyrazine, all exhibit intense metal to ligand charge transfer (MLCT) based transitions in the visible but possess lower lying metal to metal charge transfer (MMCT) excited states. These supramolecular complexes with low lying MMCT states photocleave DNA when excited into their intense MLCT transitions. Structurally similar complexes without this low lying MMCT state do not exhibit DNA photocleavage, establishing the role of this MMCT state in the DNA photocleavage event. Design considerations necessary to produce functional DNA photocleavage agents are presented herein.

Citations

• Synthesis and Study of Ru,Rh,Ru Triads:  Modulation of Orbital Energies in a Supramolecular Architecture
• Visible Light Induced Photocleavage of DNA by a Mixed-Metal Supramolecular Complex:  [(bpy)₂Ru(dpp)₂RhCl₂]⁵⁺

Cited by

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• Preferential DNA cleavage under anaerobic conditions by a DNA-binding ruthenium dimer. [europepmc]
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• Synthesis, characterization and biological activity of trans-platinum(II) complexes with chloroquine. [europepmc]
• Preliminary anti-cancer photodynamic therapeutic in vitro studies with mixed-metal binuclear ruthenium(II)-vanadium(IV) complexes. [europepmc]
• Control and utilization of ruthenium and rhodium metal complex excited states for photoactivated cancer therapy. [europepmc]
• Transition Metal Complexes and Photodynamic Therapy from a Tumor-Centered Approach: Challenges, Opportunities, and Highlights from the Development of TLD1433. [europepmc]
• Synthesis, characterization, DNA binding, topoisomerase inhibition, and apoptosis induction studies of a novel cobalt(III) complex with a thiosemicarbazone ligand. [europepmc]
• Bis[pyrrolyl Ru(ii)] triads: a new class of photosensitizers for metal-organic photodynamic therapy. [europepmc]

Related

• Visible Light Induced Photocleavage of DNA by a Mixed-Metal Supramolecular Complex:  [(bpy)₂Ru(dpp)₂RhCl₂]⁵⁺
• Intercalation Favors DNA Covalent Photobinding in Photoresponsive Dual PDT/PCT Bimetallic Assemblies
• Transition Metal Complexes and Photodynamic Therapy from a Tumor-Centered Approach: Challenges, Opportunities, and Highlights from the Development of TLD1433
• Synthesis and Study of Ru,Rh,Ru Triads:  Modulation of Orbital Energies in a Supramolecular Architecture
• Photobiological Impact of [(bpy)₂Ru(dpp)₂RhCl₂]Cl₅ and [(bpy)₂Os(dpp)₂RhCl₂]Cl₅ [bpy = 2,2‘-Bipyridine; dpp = 2,3-Bis(2-pyridyl)pyrazine] on Vero Cells