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Long-Range Electron and Hole Transport through DNA with Tethered Cyclometalated Iridium(III) Complexes

Shao, Fangwei and Barton, Jacqueline K. (2007) Long-Range Electron and Hole Transport through DNA with Tethered Cyclometalated Iridium(III) Complexes. Journal of the American Chemical Society, 129 (47). pp. 14733-14738. ISSN 0002-7863. doi:10.1021/ja0752437. https://resolver.caltech.edu/CaltechAUTHORS:20160226-135927080

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Abstract

A cyclometalated complex of Ir(III) is covalently tethered to DNA oligonucleotides and serves as both a photooxidant and photoreductant in the study of DNA-mediated hole transport (HT) and electron transport (ET). Spectroscopic and melting temperature studies support intercalation of the tethered complex into the DNA duplex through the functionalized dppz ligand. Using these tethered assemblies, ET and HT is initiated in DNA by the same photoredox probe. Cyclopropylamine substituted bases, N_4-cyclopropylcytosine (^(CP)C) and N_2-cyclopropylguanine (^(CP)G) are used as kinetically fast electron and hole traps to probe the resulting electron migration processes after direct irradiation of the tethered Ir assembly. Oxidation of ^(CP)G and ^(CP)C is promoted efficiently by HT from photoexcited Ir(III) when the modified bases are positioned in the purine strands of the A-tract. In contrast, when CPC is embedded in a pyrimidine tract, ET to yield reductive decomposition is observed. Thus, the Ir(III)-tethered DNA assembly containing cyclopropyl-modified bases provides a unique model system to explore the two DNA-mediated electron migration processes using the same photoredox probe and the same DNA bridge.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja0752437DOIArticle
ORCID:
AuthorORCID
Shao, Fangwei0000-0003-2007-3920
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 2007 American Chemical Society. Received July 13, 2007. Publication Date (Web): November 7, 2007. We are grateful to the NIH (Grant GM49216) for their financial support of this work.
Funders:
Funding AgencyGrant Number
NIHGM49216
Issue or Number:47
DOI:10.1021/ja0752437
Record Number:CaltechAUTHORS:20160226-135927080
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160226-135927080
Official Citation:Long-Range Electron and Hole Transport through DNA with Tethered Cyclometalated Iridium(III) Complexes Fangwei Shao and Jacqueline K. Barton Journal of the American Chemical Society 2007 129 (47), 14733-14738 DOI: 10.1021/ja0752437
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:64810
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:29 Feb 2016 18:16
Last Modified:10 Nov 2021 23:35

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