High-Symmetry Anthradithiophene Molecular Packing Motifs Promote Thermally Activated Singlet Fission
نویسندگان
چکیده
When considering the optimal molecular packing to realize charge multiplication in organic photovoltaic materials, subtle changes intermolecular transfer (CT) coupling can strongly modulate singlet fission. To understand why certain arrangements are more conducive by triplet pair (TT) formation, we measure diffraction-limited transient absorption (TA) response from four single-crystal functionalized derivatives of fluorinated anthradithiophene: diF R-ADT (R = TES, TSBS, TDMS, TBDMS). TES-ADT and TDMS-ADT both exhibit 2D brickwork structures, TSBS-ADT adopts a 1D sandwich-herringbone structure, TBDMS-ADT exhibits twisted-columnar structure. or single crystals resonantly probed parallel their (CT)-axis projections, TA signal is dominated rising component on picosecond time scale (rate kTT), attributed TT state population. orthogonal CT-axis, instead recover falling kinetics depletion at rate kA. The ratio estimates formation efficiency, ?TT kTT/kA relative exciton self-trapping. ranged near 100% 84% TDMS-ADT. Interestingly, only manifest CT-mediated self-trapping depletion. Singlet fission prohibitive owing its lower symmetry that leads S1 CT-state energy separation ?3× larger than other packings. Collectively, these results highlight configurations either enhance completely suppress formation.
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ژورنال
عنوان ژورنال: Journal of Physical Chemistry C
سال: 2022
ISSN: ['1932-7455', '1932-7447']
DOI: https://doi.org/10.1021/acs.jpcc.1c10977