RESUMEN
The quintet triplet-pair state may be generated upon singlet fission and is a critical intermediate that dictates the fate of excitons, which can be exploited for photovoltaics, information technologies, and biomedical imaging. In this report, we demonstrate that continuous-wave and pulsed electron spin resonance techniques such as phase-inverted echo-amplitude detected nutation (PEANUT), which have emerged as the primary tool for identifying the spin pathways in singlet fission, probe fundamentally different triplet-pair species. We directly observe that the generation rate of high-spin triplet pairs is dependent on the molecular orientation with respect to the static magnetic field. Moreover, we demonstrate that this observation can prevent incorrect analysis of continuous-wave electron spin resonance (cw-ESR) measurements and provide insight into the design of materials to target specific pathways that optimize exciton properties for specific applications.
RESUMEN
Several recent electron spin resonance studies have observed a quintet multiexciton state during the singlet fission process. Here, we provide a general theoretical explanation for the generation of this state by invoking a time-varying exchange coupling between pairs of triplet excitons and subsequently solving the relevant time-varying spin Hamiltonian for different rates at which the exchange coupling varies. We simulate experimental ESR spectra and draw qualitative conclusions about the adiabatic and diabatic transitions between triplet pair spin states.
RESUMEN
Singlet fission is an exciton multiplication process that allows for the conversion of one singlet exciton into two triplet excitons. Organic semiconductors, such as acenes and their soluble bis(triisopropylsilylethynyl) (TIPS) substituted counterparts, have played a major role in elucidating the understanding of the underlying mechanisms of singlet fission. Despite this, one prominent member of the acene family that has received little experimental attention to date is TIPS-anthracene, even with computational studies suggesting potential high singlet fission yields in the solid state. Here, time-resolved spectroscopic and magneto-photoluminescence measurements were performed on spin-cast films of TIPS-anthracene, showing evidence for singlet fission. A singlet fission yield of 19% (out of 200%) is estimated from transient absorption spectroscopy. Kinetic modeling of the magnetic field effect on photoluminescence suggests that fast rates of triplet dissociation lead to a low magnetic photoluminescence effect and that non-radiative decay of both the S1 and 1(TT) states is the cause for the low triplet yield.