TY - JOUR
T1 - Synthesis of Soluble Dinaphtho[2,3- b:2′,3′- f]thieno[3,2- b]thiophene (DNTT) Derivatives
T2 - One-Step Functionalization of 2-Bromo-DNTT
AU - Kawabata, Kohsuke
AU - Usui, Sayaka
AU - Takimiya, Kazuo
N1 - Funding Information:
This work was supported by JSPS KAKENHI Grant Numbers JP17H07363 (K. K.), JP19H00906 (K. T.). We acknowledge the Center for Computational Materials Science, Institute for Materials Research, Tohoku University for the use of MASAMUNE-IMR. HRMS and elemental analysis were carried out at the Materials Characterization Support Unit, Advanced Technology Support Division and Materials Characterization Support Unit in RIKEN Center for Emergent Matter Science, and Research and Analytical Center for Giant Molecules in Tohoku University.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2020/1/3
Y1 - 2020/1/3
N2 - For developing dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT) derivatives as solution processable organic semiconductors, we synthesized 2-brominated DNTT (Br-DNTT) as a common precursor to 2-substituted DNTT derivatives. The synthesis of Br-DNTT features chemoselective metalation and cross-coupling reactions that enable us to keep the 2-bromo group intact from the starting material, 2-bromo-6-methoxynaphthalene, to Br-DNTT. We demonstrated one-step functionalization of Br-DNTT by various palladium- and copper-catalyzed cross-coupling reactions to introduce a variety of substituents, including ethynyl, aryl, heteroaryl, alkyl, alkoxy, and alkylthio groups, in yields of 73 to 98%. The resulting 12 examples of 2-substituted DNTT derivatives, which have bulky or flexible solubilizing groups, have improved solubilities of up to 200 times the solubility of unsubstituted DNTT. Some of the soluble 2-substituted DNTT derivatives were applied to the solution-processed fabrication of organic field-effect transistor (OFET) devices. Most of the OFET devices exhibited average hole mobilities in the order of 10-1 to 10-2 cm2 V-1 s-1. Among the DNTT derivatives, the one substituted with 4-(2-(2-methoxyethoxy)ethoxy)butyl group has the highest solubility of 8.45 g L-1 and also exhibited the highest average hole mobility of 0.28 cm2 V-1 s-1 in the OFET devices.
AB - For developing dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT) derivatives as solution processable organic semiconductors, we synthesized 2-brominated DNTT (Br-DNTT) as a common precursor to 2-substituted DNTT derivatives. The synthesis of Br-DNTT features chemoselective metalation and cross-coupling reactions that enable us to keep the 2-bromo group intact from the starting material, 2-bromo-6-methoxynaphthalene, to Br-DNTT. We demonstrated one-step functionalization of Br-DNTT by various palladium- and copper-catalyzed cross-coupling reactions to introduce a variety of substituents, including ethynyl, aryl, heteroaryl, alkyl, alkoxy, and alkylthio groups, in yields of 73 to 98%. The resulting 12 examples of 2-substituted DNTT derivatives, which have bulky or flexible solubilizing groups, have improved solubilities of up to 200 times the solubility of unsubstituted DNTT. Some of the soluble 2-substituted DNTT derivatives were applied to the solution-processed fabrication of organic field-effect transistor (OFET) devices. Most of the OFET devices exhibited average hole mobilities in the order of 10-1 to 10-2 cm2 V-1 s-1. Among the DNTT derivatives, the one substituted with 4-(2-(2-methoxyethoxy)ethoxy)butyl group has the highest solubility of 8.45 g L-1 and also exhibited the highest average hole mobility of 0.28 cm2 V-1 s-1 in the OFET devices.
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U2 - 10.1021/acs.joc.9b02585
DO - 10.1021/acs.joc.9b02585
M3 - Article
C2 - 31762281
AN - SCOPUS:85075788555
VL - 85
SP - 195
EP - 206
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 1
ER -