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A spectroscopic study and design of novel iron-platinum mixed-valence charge transfer complexes

Posted on:2006-08-16Degree:Ph.DType:Thesis
University:Princeton UniversityCandidate:Mordas, Carolyn JFull Text:PDF
GTID:2451390005495097Subject:Chemistry
Abstract/Summary:
The work in the first half of this thesis involved the use of modern spectroscopic tools to probe the behavior of iron-platinum intervalent charge transfer complexes. The degree of electronic coupling between two acceptor species of two related hexanuclear charge transfer species was investigated using ultrafast pump-probe and resonance Raman spectroscopy. Excited state lifetimes were determined for both hexanuclear species, and these results were compared to the trinuclear complex.; The development of ultrafast pulses of spectrally broad light and its applications in ultrafast pump-probe spectroscopy was also investigated. The charge-transfer dynamics of a trinuclear Fe-Pt-Fe complex have previously been investigated using one or two-color pump-probe spectroscopy, and the development of femtosecond pulses of white light can enable the observation of a broad range of wavelengths (excited state absorption spectrum) as a function of delay time of the pump pulse for these complexes. Generation of white-light pulses by femtosecond pulses through sapphire crystal was well established, however, the range of wavelengths does not provide good coverage of the blue portion of the optical spectrum. Generation of ultrafast white light continua with both calcium fluoride and sapphire was studied in detail.; The second half of this thesis involved the synthesis and characterization of novel trinuclear complexes and a study of their photochemistry. In addition, the application of these complexes to chemotherapy is discussed. The previous well-known [(NC)5FeII-CN-PtIV(NH 3)4-NC-FeII(CN)5]4- is able to undergo photodissociation to form a square planar [Pt II(NH3)4]2+ complex, similar to cisplatin, PtII(NH3)2Cl2, a widely used and potent chemotherapy agent. The synthesis of two trinuclear intervalent trinuclear charge-transfer complexes with a dichloro-diammine-platinum center that can be activated to form cisplatin locally with visible light were synthesized, characterized and their photochemistry was investigated.
Keywords/Search Tags:Charge transfer, Complexes, Investigated, Light
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