The photoactivation of Ru(II) complexes have been used in a number of applications, including solar energy conversion, sensors, and photoinduced drug delivery. The triplet metal-to-ligand charge transfer (3MLCT) excited state in these complexes is typically deactivated through a thermally accessible triplet metal-centered, ligand-field state (3LF). While a high-energy 3LF state is necessary to achieve a long-lived, emissive 3MLCT state for apllications that require energy/charge transfer, a low-lying 3LF state is desirable for the efficient drug delivery. Therefore, understanding the structural and electronic molecular features that affect the relative energies of these states is critical for optimizing the desired excited state properties for a given purpose. Properties desirable for optimizing the performance of these complexes will be discussed, along with examples of complexes that are able to both release a drug molecule upon irradiation and produce singlet oxygen to achieve cell death. These dual activity complexes are significantly more active than those that can either photorelease drugs or generate singlet oxygen.
Dirhodium(II,II) complexes are shown to possess excited states accessible with visible to near-IR light that are able to undergo reactivity for applications ranging from photochemotherapy to solar energy conversion. In particular, cis– [Rh2(DPhF)2(bncn)2]2+ (DPhF = N,N'-diphenylformamidinate, bncn = benzocinnoline; 1) is able to act as a single-molecule photocatalyst for the generation of hydrogen from acidic solutions in the presence of a sacrificial electron donor when irradiated with red/near-IR light. The water solubility of 1 led us to investigate its photoreactivity towards DNA. Complex 1 is able to photocleave DNA at pH = 5.3 upon irradiation with visible light, however, no photocleavage is observed at neutral pH. The binding of 1 to DNA was investigated and likely interacts with the polyanionic double helix through multiple modes, including electrostatic interactions, covalent coordination, and/or partial intercalation.
Access to the requested content is limited to institutions that have purchased or subscribe to SPIE eBooks.
You are receiving this notice because your organization may not have SPIE eBooks access.*
*Shibboleth/Open Athens users─please
sign in
to access your institution's subscriptions.
To obtain this item, you may purchase the complete book in print or electronic format on
SPIE.org.
INSTITUTIONAL Select your institution to access the SPIE Digital Library.
PERSONAL Sign in with your SPIE account to access your personal subscriptions or to use specific features such as save to my library, sign up for alerts, save searches, etc.