ABSTRACT
We investigated the optical properties of 4,4'-stilbenedinitrene at low temperature and in high magnetic fields and compared the results with complementary first principles calculations. Both physical tuning parameters allow us to manipulate the singlet-triplet equilibrium, and by doing so, control the optical contrast (which is on the order of -2.5 × 10(2) cm(-1) at 555 nm and 35 T). Moreover, analysis of the magneto-optical response using a combined population and Beer's law framework reveals the singlet-triplet spin gap and identifies particular features in the absorption difference spectrum as deriving from singlet or triplet state excitations. These findings deepen our understanding of coupling in open shell molecules and show how chemical structure modification can modulate charge-spin interactions in organic biradicals.
Subject(s)
Magnetic Fields , Stilbenes/chemistry , Molecular Structure , TemperatureABSTRACT
We investigated the tunability of the singlet-triplet equilibrium population in the organic biradical 1,4-phenylenedinitrene via magneto-optical spectroscopy. A rich magnetochromic response occurs because applied field increases the concentration of the triplet state species, which has a unique optical signature by comparison with the singlet biradical and the precursor molecule. A Curie-like analysis of the magneto-optical properties allows us to extract the spin gap, which is smaller than previously supposed. These measurements establish the value of local-probe photophysical techniques for magnetic property determination in open-shell systems such as biradicals where a traditional electron paramagnetic resonance Curie law analysis has intrinsic limitations.
ABSTRACT
We report high resolution 15N NMR probing of the solid-solid phase transition of 15N-labeled ammonia borane (NH3BH3) at 225 K. Both the 15N isotropic chemical shift (delta iso) and the spin-lattice relaxation rate (T1-1) exhibited strong anomalies around 225 K. The analysis of T1-1 using the Bloembergen, Purcell, and Pound model showed that the motional correlation time, tau, increased from about 1 to 100 ps and the corresponding Arrhenius activation energy increased from 6 to 14.5 kJ/mol on going through the transition toward lower temperatures. The temperature dependence of delta iso was interpreted by an extension of the Bayer model. The time scale of the underlying motion was found to be in a reasonable agreement with the T1-1 data. These results imply that the NH3 rotor motion plays a pivotal role in the transition mechanism and that the transition is of both order-disorder and displacive type.
