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Side-chain
sequence enabled regioisomeric acceptors, bearing different
side-chain sequences on the same conjugated backbone, are herein reported.
Two regioregular polymers PTBI-1 and PTBI-2 and one regiorandom polymer
PTBI-3 were synthesized from these two regioisomeric acceptors for
a comparative study. UV–vis–NIR absorption spectroscopy
and electrochemical study confirmed similar frontier molecular orbital
levels of the three polymers in their solid state. More intriguingly,
absorption profiles suggest that the sequence of side chains greatly
governs the aggregation behaviors. Furthermore, the PTBI-2 film shows
larger ordered domains than PTBI-1 and PTBI-3 films, as supported
by AFM and GIWAXS measurements. As a result, PTBI-2-based FET devices
achieved an average hole mobility of 1.37 cm2 V–1 s–1, much higher than the two polymers with other
side-chain sequences. The regiorandom PTBI-3 exhibited the lowest
average hole mobility of 0.27 cm2 V–1 s–1. This study highlights the significant impact
of side-chain sequence regioisomerism on aggregation behaviors, morphologies,
and subsequently charge transport properties of donor–acceptor
type conjugated polymers.
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