Molecular engineering of tetraazapentacene with different numbers of fluorine and chlorine substituents fine-tunes the frontier molecular orbitals, molecular vibrations, and π-π stacking for n-type organic semiconductors. Among the six halogenated tetraazapentacenes studied herein, the tetrachloro derivative (4Cl-TAP) in solution-processed thin-film transistors exhibits electron mobility of 14.9 ± 4.9 cm V s with a maximum value of 27.8 cm V s , which sets a new record for n-channel organic field-effect transistors. Computational studies on the basis of crystal structures shed light on the structure-property relationships for organic semiconductors. First, chlorine substituents slightly decrease the reorganization energy of the tetraazapentacene whereas fluorine substituents increase the reorganization energy as a result of fine-tuning molecular vibrations. Second, the electron transfer integral is very sensitive to subtle changes in the 2D π-stacking with brickwork arrangement. The unprecedentedly high electron mobility of 4Cl-TAP is attributed to the reduced reorganization energy and enhanced electron transfer integral as a result of modification of tetraazapentacene with four chlorine substituents.
Herein we report
the synthesis, crystal structures, and semiconductor
properties of new derivatives of bisnaphtho[2′,3′:3,4]cyclobut[1,2-b:1′,2′-i]anthracene
(BNCBA). It is found that the π–π stacking of BNCBA
in single crystals can be largely modified by alkyl substituting groups
of different lengths. In particular, the tetrahexyl derivative exhibits
π–π stacking with an unusual zigzag arrangement.
The variation of molecular packing also leads to a change in charge
transport characteristics as found from the theoretical calculation
of mobility on the basis of single-crystal structures. All of these
BNCBA derivatives function as p-type semiconductors in solution-processed
thin film transistors, and the tetrahexyl derivative exhibits a field
effect mobility as high as 2.9 cm2/(V s).
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