Charge Photoinjection in Intercalated and Covalently Bound [Re(CO)3(dppz)(py)]+鈥揇NA Constructs Monitored by Time-Resolved Visible and Infrared Spectroscopy
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- 作者：Eric D. Olmon ; Pamela A. Sontz ; Ana Mar铆a Blanco-Rodr铆guez ; Michael Towrie ; Ian P. Clark ; Anton铆n Vl膷ek ; Jr. ; Jacqueline K. Barton
- 刊名：Journal of the American Chemical Society
- 出版年：2011
- 出版时间：August 31, 2011
- 年：2011
- 卷：133
- 期：34
- 页码：13718-13730
- 全文大小：1050K
- 年卷期：v.133,no.34(August 31, 2011)
- ISSN：1520-5126
文摘
The complex [Re(CO)3(dppz)(py鈥?OR)]+ (dppz = dipyrido[3,2-<i>ai>:2鈥?3鈥?<i>ci>]phenazine; py鈥?OR = 4-functionalized pyridine) offers IR sensitivity and can oxidize DNA directly from the excited state, making it a promising probe for the study of DNA-mediated charge transport (CT). The behavior of several covalent and noncovalent Re鈥揇NA constructs was monitored by time-resolved IR (TRIR) and UV/visible spectroscopies, as well as biochemical methods, confirming the long-range oxidation of DNA by the excited complex. Optical excitation of the complex leads to population of MLCT and at least two distinct intraligand states. Experimental observations that are consistent with charge injection from these excited states include similarity between long-time TRIR spectra and the reduced state spectrum observed by spectroelectrochemistry, the appearance of a guanine radical signal in TRIR spectra, and the eventual formation of permanent guanine oxidation products. The majority of reactivity occurs on the ultrafast time scale, although processes dependent on slower conformational motions of DNA, such as the accumulation of oxidative damage at guanine, are also observed. The ability to measure events on such disparate time scales, its superior selectivity in comparison to other spectroscopic techniques, and the ability to simultaneously monitor carbonyl ligand and DNA IR absorption bands make TRIR a valuable tool for the study of CT in DNA.