Premium
Synthesis of Thiophene‐annulated Naphthalene Diimide‐based Small‐Molecular Acceptors via Two‐step C−H Activation
Author(s) -
Matsidik Rukiya,
Takimiya Kazuo
Publication year - 2019
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201801655
Subject(s) - stille reaction , thiophene , diimide , chemistry , suzuki reaction , naphthalene , halogenation , photochemistry , combinatorial chemistry , anthracene , aryl , polymer chemistry , catalysis , molecule , organic chemistry , perylene , palladium , alkyl
Thiophene‐annulated naphthalene diimide (NTI)‐based molecules have recently emerged as an important class of n‐type electronic materials. However, their synthesis has predominantly been achieved by Stille or Suzuki coupling reactions despite the presence of a potential C−H bond in NTI. Additionally, the synthesis of NTI or more generally mono‐functionalization of naphthalene diimide (NDI) starts with a cumbersome bromination that results in a low yield, is unselective, and requires tedious purification. We herein thus address these issues via a two‐step C−H activation: a rhodium‐catalyzed direct C−H iodinization is first presented for NDI, followed by establishing an efficient direct arylation protocol for NTI with high yield and robustness. Coupling of up to four NTI units on a benzene or pyrene core is demonstrated along with other aryl bromide substrates. All the herein reported NTI‐based small molecules showed n‐type semiconductor behavior under air.