Two Isomeric Azulene-Decorated Naphthodithiophene Diimide-based Triads: Molecular Orbital Distribution Controls Polarity Change of OFETs Through Connection Position

Altering the charge carrier transport polarities of organic semiconductors by molecular orbital distribution has gained great interest. Herein, we report two isomeric azulene-decorated naphthodithiophene diimide (NDTI)-based triads (e.g., NDTI-B2Az and NDTI-B6Az), in which two azulene units were connected with NDTI at the 2-position of the azulene ring in NDTI-B2Az, whereas two azulene units were incorporated with NDTI at the 6-position of the azulene ring in NDTI-B6Az. The two isomeric triads were excellently soluble in common organic solvents. Density functional theory calculations on the molecular orbital distributions of the triads reveal that the lowest unoccupied molecular orbitals are completely delocalized over the entire molecule for both NDTI-B2Az and NDTI-B6Az, indicating great potential for n-type transport behavior, whereas the highest occupied molecular orbitals are mainly delocalized over the entire molecule for NDTI-B2Az or only localized at the two terminal azulene units for NDTI-B6Az, implying great potential for p-type transport behavior for the former and a disadvantage of hole carrier transport for the latter. Under ambient conditions, solution-processed bottom-gate top-contact transistors based on NDTI-B2Az showed ambipolar field-effect transistor (FET) characteristics with high electron and hole mobilities of 0.32 (effective electron mobility approximate to 0.14 cm(2) V-1 s(-1) according to a reliability factor of 43%) and 0.03 cm(2) V-1 s(-1) (effective hole mobility approximate to 0.01 cm(2) V-1 s(-1) according to a reliability factor of 33%), respectively, whereas a typically unipolar n-channel behavior is found for a film of NDTI-B6Az with a high electron mobility up to 0.13 cm(2) V-1 s(-1) (effective electron mobility approximate to 0.06 cm(2) V-1 s(-1) according to a reliability factor of 43%). The results indicate that the polarity change of organic FETs based on the two isomeric triads could be controlled by the molecular orbital distributions through the connection position between the azulene unit and NDTI.