In the Bocarsly group, we affectionately refer to [(NC)6Fe(II)-CN-Pt(IV)(NH3)4-NC-Fe(II)(CN)6]4- as "trimer." This complex undergoes a two-electron intervalent chargetransfer process. When a single photon is absorbed, an electron is transferred from one of the Fe(II) centers to the Pt(IV) center, yielding a short-lived Fe(II)-Pt(III)-Fe(III) intermediate. An electron is then transferred from the remaining Fe(II) center to the Pt(III) center, resulting in the dissociation of the complex into 2[Fe(III)(CN)63-] and Pt(NH3)42+. Thus, the absorption of a single photon gives rise to the transfer of two electrons.
Previous studies of trimer and related systems:
- Crystal structure determination of the Pt(NH3)42+ salt of trimer.
- Investigation of ground and excited state energetics of trimer andseveral closely-related complexes using classical Marcus-Hush electron transfer theory and a resonance Raman intensity analysis.
- Polymerization of trimer onto transparent conductive surfaces and the photolithographic properties of these sytems. Selectivity of electron transfer processes within oligomeric and polymeric chains insolution and on surfaces.
- Surface-attachment of trimer to TiO2 nanoparticles and investigation of the photoinduced electron transfer processes in these sytems.
- Photolithography in a trimer-based "cyanogel" sol-gel system.
- Transient absorption spectroscopy to probe the lifetime of the proposed FeII-PtIII-FeIII intermediate using both 400nm and 530nm as probe wavelengths.
- Pt-ligand replacements to enable the generation of cis-platin upon photodissociation, and Fe-ligand replacements to affect the solubility.
Recent research involving trimer
- Continuation of pump-probe spectroscopy of trimer and related intervalent charge transfer complexes.
- Excited state absorption measurements on trimer and related compounds using femtosecond white light generation with calcium fluoride.
