A previously unreported polymorph of 5,11-bis(triisopropylsilylethynyl)anthradithiophene
(TIPS ADT), Form II, crystallizes from melt-processed TIPS ADT films
blended with 16 ± 1 wt % medium density polyethylene (PE). TIPS
ADT/PE blends that initially are crystallized from the melt produce
twisted TIPS ADT crystals of a metastable polymorph (Form IV, space
group P1̅) with
a brickwork packing motif distinct from the slipstack packing by solution-processed
TIPS ADT crystals (Form I, space group P21/c) at room temperature. When these films were cooled
to room temperature and subsequently annealed at 100 °C, near
a PE melting temperature of 110 °C, Form II crystals nucleated
and grew while consuming Form IV. The growth rate and orientations
of Form II crystals were predetermined by the twisting pitch and growth
direction of the original banded spherulites in the melt-processed
films of the blends. Notably, the Form IV → II transition was
not observed during thermal annealing of neat TIPS ADT films without
PE. The presence of the mobile PE phase during thermal annealing of
TIPS ADT/PE blend films increases the diffusion rate of TIPS ADT molecules,
and the rate of nucleation of Form II. Form IV crystals are more conductive
but less emissive compared to Form II crystals.