Excited State Electron Transfer of All-Inorganic Heterobinuclear TiOMn2+ Chromophore Anchored on Silica Nanoparticle Surface
| Autor: | Beth Anne McClure, Heinz Frei |
|---|---|
| Rok vydání: | 2014 |
| Předmět: |
Coupling constant
Materials science Analytical chemistry Activation energy Chromophore Surfaces Coatings and Films Electronic Optical and Magnetic Materials Electron transfer General Energy Absorption band Excited state Yield (chemistry) Ultrafast laser spectroscopy Physical and Theoretical Chemistry |
| Zdroj: | The Journal of Physical Chemistry C. 118:11601-11611 |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/jp503196w |
| Popis: | The oxo-bridged heterobinuclear chromophore TiOMn2+ has been covalently anchored onto a silica nanoparticle surface, allowing for the preparation of optically transparent solid state samples. Optical spectra of the material yield a broad metal-to-metal charge-transfer (MMCT) transition in the UV with a tail extending to 550 nm. Fitting the absorption band to a Gaussian curve gives a maximum at 44 610 (±230) cm–1 (587 (±20) M–1 cm–1) with a full width at half-maximum of 17 320 (±160) cm–1, and yields an electronic coupling constant, HABopt, of 4200 cm–1 by Hush analysis. Transient absorption measurements of transparent pressed pellets in vacuum yield a 2.43 (±0.20) μs lifetime at room temperature. The temperature dependence of the lifetime in the range of 10–40 °C gives an activation energy of 1.67 (±0.36) kcal/mol and pre-exponential factor A of 7.3 (±4.4) × 106 s–1. This temperature dependence results in an electronic coupling constant HABkin of less than 1 cm–1. The disparity between the large electroni... |
| Databáze: | OpenAIRE |
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