A Kinetic Model for Photoswitching of magnetism in the High Spin Molecule [Mo(IV)(CN)2(CN-Cu(II)(tren))6](ClO4)8
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en
Article de revue
Este ítem está publicado en
Physical Chemistry Chemical Physics. 2008, vol. 10, n° 35, p. 5469-5474
Royal Society of Chemistry
Resumen en inglés
The heptanuclear complex [Mo(IV)(CN)2(CN-CuL)6]8+ exhibits photomagnetism. An earlier microscopic model showed that the transition dipole moments for excitation in different spin manifolds are similar in magnitude. In this ...Leer más >
The heptanuclear complex [Mo(IV)(CN)2(CN-CuL)6]8+ exhibits photomagnetism. An earlier microscopic model showed that the transition dipole moments for excitation in different spin manifolds are similar in magnitude. In this paper, we attribute photomagnetism to the long lived S=3 charge transfer excited state for which there appears to be sufficient experimental evidence. We model the photomagnetism by employing a kinetic model which includes internal conversions and intersystem crossings. The key feature of the model is assumption of the existence of two kinds of S=3 states: one which has no direct pathway for internal conversion and the other characterized by slow kinetics for internal conversion to the low-energy states. The trapped S=3 state can decay via a thermally activated barrier to the other S=3 state. The experimental temperature dependence of magnetization plot is fitted using rate constants with Arrhenius dependence. The two different experimental cMT vs. T curves obtained with different irradiation times are fitted with our model. Our studies show that the photomagnetism in these systems is governed by kinetics and not due to differences in oscillator strengths for excitation of the different spin states.< Leer menos
Palabras clave en inglés
Kinetic
Magnetism
High spin
Molecule
Chemical compounds
Orígen
Importado de HalCentros de investigación