Three unsymmetrical diiodobichalcogenophenes SSeI2, STeI2, and SeTeI2 and a diiodoterchalcogenophene SSeTeI2 were prepared to synthesize a new class of polychalcogenophenes with precisely controlled sequences by catalyst-transfer polycondensation.
Two
types of pyrenes are incorporated randomly into P(NDI2OD-T2).
For the resultant polymers, the growth in the pyrene quantity results
in the reduction of π-order. The decrease in π-order does
not inevitably depreciate the organic field-effect transistor (OFET)
mobility. A competitive mechanism between molecular fractionation
and naphthalene diimide (NDI)–pyrene interactions is proposed.
For moderate pyrene incorporation, molecular fractionation is dominant.
Form I crystallites are fragmented, increasing the rigid amorphous
fraction (RAF) regions. As for high pyrene content, the NDI–pyrene
interactions take the lead, facilitating the establishment of a form
II polymorph. The RAF can strengthen the interconnection among polymer
crystallites. Overall, this work demonstrates a novel approach to
intensifying the intrachain interconnection among polymers by the
donor–acceptor (i.e., NDI–pyrene) complementary
interactions, offering pathways for efficient charge transporting
in OFETs.
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