Direct Observation of Correlated Triplet Pair Dynamics during Singlet Fission Using Ultrafast Mid-IR Spectroscopy

Abstract

Singlet fission is an exciton multiplication mechanism in organic materials whereby high energy singlet excitons can be converted into two triplet excitons with near unity quantum yields. As new singlet fission sensitizers are developed with properties tailored to specific applications, there is an increasing need for design rules to understand how the molecular structure and crystal packing arrangements influence the rate and yield with which spin-correlated intermediates known as correlated triplet pairs can be successfully separated—a prerequisite for harvesting the multiplied triplets. Toward this end, we identify new electronic transitions in the mid-infrared spectral range that are distinct for both initially excited singlet states and correlated triplet pair intermediate states using ultrafast mid-infrared transient absorption spectroscopy of crystalline films of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-Pn). We show that the dissociation dynamics of the intermediates can be measured throu...