Modulation of ligand fluorescence by the Pt(II)/Pt(IV) redox couple
Dedicated to Professor Jon Zubieta on the occasion of his 65th birthday.
| Main Authors: | , |
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| Format: | Article |
| Language: | en_US |
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Elsevier
2016
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| Online Access: | http://hdl.handle.net/1721.1/105335 https://orcid.org/0000-0002-2693-4982 |
| _version_ | 1811095550013997056 |
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| author | Wilson, Justin Jeff Lippard, Stephen J. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Wilson, Justin Jeff Lippard, Stephen J. |
| author_sort | Wilson, Justin Jeff |
| collection | MIT |
| description | Dedicated to Professor Jon Zubieta on the occasion of his 65th birthday. |
| first_indexed | 2024-09-23T16:19:17Z |
| format | Article |
| id | mit-1721.1/105335 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T16:19:17Z |
| publishDate | 2016 |
| publisher | Elsevier |
| record_format | dspace |
| spelling | mit-1721.1/1053352022-10-02T07:42:54Z Modulation of ligand fluorescence by the Pt(II)/Pt(IV) redox couple Wilson, Justin Jeff Lippard, Stephen J. Massachusetts Institute of Technology. Department of Chemistry Lippard, Stephen J. Wilson, Justin Jeff Lippard, Stephen J. Dedicated to Professor Jon Zubieta on the occasion of his 65th birthday. The dangling carboxylic acid moiety of the known platinum(II) complex, [Pt(edma)Cl2] (edma = ethylenediaminemonoacetic acid), was functionalized via amide coupling chemistry with benzyl amine and dansyl ethylenediamine to afford the derivatives [Pt(edBz)Cl2] (1) and [Pt(edDs)Cl2] (2). Subsequent oxidation of these platinum(II) complexes with iodobenzene dichloride in DMF yielded the respective platinum(IV) analogs, [Pt(edBz)Cl4] (3) and [Pt(edDs)Cl4] (4). All four platinum complexes were characterized by multinuclear NMR spectroscopy, IR spectroscopy, electrospray ionization mass spectrometry, and elemental analysis. In addition, compounds 1 and 3 were structurally characterized by X-ray crystallography. The photophysical properties of the compounds bearing the fluorescent dansyl moiety, 2 and 4, were evaluated. The emission quantum yields of 2 and 4 in DMF are 27% and 1.6%, respectively. This large difference in emission efficiency indicates that the platinum(IV) center in 4 is more effective at quenching the dansyl-based fluorescence than the platinum(II) center in 2. Time-dependent density functional theory calculations indicate that 4 has several low-lying singlet excited states that energetically lie below the primary radiation-accessible excited state of the dansyl fluorophore. These low-energy excited states may offer non-radiative decay pathways that lower the overall emission quantum yield. Treatment of 4 with biologically relevant reducing agents in pH 7.4 phosphate-buffered saline induces a 6.3-fold increase in emission intensity. These results demonstrate that 4 and future derivatives thereof may be useful for imaging the reduction of platinum(IV) complexes in living systems, chemistry of importance for evolving platinum-based anticancer drug strategies. National Cancer Institute (U.S.) (grant CA034992) National Institutes of Health (U.S.) (NIH Grant 1S10RR13886-01) 2016-11-15T20:15:18Z 2016-11-15T20:15:18Z 2012-01 Article http://purl.org/eprint/type/JournalArticle 00201693 http://hdl.handle.net/1721.1/105335 Wilson, Justin J., and Stephen J. Lippard. “Modulation of Ligand Fluorescence by the Pt(II)/Pt(IV) Redox Couple.” Inorganica Chimica Acta 389 (July 2012): 77-84. https://orcid.org/0000-0002-2693-4982 en_US http://dx.doi.org/10.1016/j.ica.2011.12.034 Inorganica Chimica Acta Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf Elsevier Prof. Lippard via Erja Kajosalo |
| spellingShingle | Wilson, Justin Jeff Lippard, Stephen J. Modulation of ligand fluorescence by the Pt(II)/Pt(IV) redox couple |
| title | Modulation of ligand fluorescence by the Pt(II)/Pt(IV) redox couple |
| title_full | Modulation of ligand fluorescence by the Pt(II)/Pt(IV) redox couple |
| title_fullStr | Modulation of ligand fluorescence by the Pt(II)/Pt(IV) redox couple |
| title_full_unstemmed | Modulation of ligand fluorescence by the Pt(II)/Pt(IV) redox couple |
| title_short | Modulation of ligand fluorescence by the Pt(II)/Pt(IV) redox couple |
| title_sort | modulation of ligand fluorescence by the pt ii pt iv redox couple |
| url | http://hdl.handle.net/1721.1/105335 https://orcid.org/0000-0002-2693-4982 |
| work_keys_str_mv | AT wilsonjustinjeff modulationofligandfluorescencebytheptiiptivredoxcouple AT lippardstephenj modulationofligandfluorescencebytheptiiptivredoxcouple |