Highly Contorted 1,2,5-Thiadiazole-Fused Aromatics for Solution-Processed Field-Effect Transistors: Synthesis and Properties.
A straightforward strategy has been used to construct 1,2,5-thiadiazole-fused 12-ring π systems through twofold Stille coupling and subsequent cyclodehydrogenation by utilizing the building blocks of naphthodithiophene and 5,6-substituted benzo[b]-2,1,3-thiadidazole. Molecules 1 a and 1 b, which exhibit highly contorted π surfaces, show a butterfly-shaped conformation according to DFT calculations. Within the molecules, a plane-to-plane angle of 44.8° was found. UV/Vis absorption, thermogravimetric analysis, differential scanning calorimetry, and cyclic voltammetry (CV) were used to study their physical properties. Strong intermolecular interactions of the nonplanar molecules were also observed by concentration-dependent (1) H NMR spectroscopy measurements and thin-film XRD characterization. The low-lying LUMO and high-lying HOMO levels of the molecules are -3.73 and -5.48 eV, respectively, as estimated from CV measurements; this indicates their potential as semiconducting materials for solution-processed organic field-effect transistors (OFETS). A field-effect hole mobility of up to 0.035 cm(2)  V(-1)  s(-1) , a threshold voltage of 6.98 V, and a current on/off ratio of 8.65×10(5) in air for 1 a have been demonstrated with the top-contact bottom-gate field-effect transistor device structures; this represents an important step toward the solution-processed OFET application of contorted aromatics.
Key Laboratory for Organic Electronics and Information Displays, Institute of Advanced Materials (IAM), Jiangsu National, Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts and Telecommunications, 9 Wenyuan Road, Nanjing, 210023, P.R. China.
Xin
X
Shi
Key Laboratory for Organic Electronics and Information Displays, Institute of Advanced Materials (IAM), Jiangsu National, Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts and Telecommunications, 9 Wenyuan Road, Nanjing, 210023, P.R. China.
Shuli
S
Liu
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China.
Chunming
C
Liu
Key Laboratory for Organic Electronics and Information Displays, Institute of Advanced Materials (IAM), Jiangsu National, Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts and Telecommunications, 9 Wenyuan Road, Nanjing, 210023, P.R. China.
Yueming
Y
Hu
Key Laboratory for Organic Electronics and Information Displays, Institute of Advanced Materials (IAM), Jiangsu National, Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts and Telecommunications, 9 Wenyuan Road, Nanjing, 210023, P.R. China.
Saihua
S
Shi
Key Laboratory for Organic Electronics and Information Displays, Institute of Advanced Materials (IAM), Jiangsu National, Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts and Telecommunications, 9 Wenyuan Road, Nanjing, 210023, P.R. China.
Nina
N
Fu
Key Laboratory for Organic Electronics and Information Displays, Institute of Advanced Materials (IAM), Jiangsu National, Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts and Telecommunications, 9 Wenyuan Road, Nanjing, 210023, P.R. China. iambmzhao@njupt.edu.cn.
Baomin
B
Zhao
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China. wangzhaohui@iccas.ac.cn.
Zhaohui
Z
Wang
Key Laboratory for Organic Electronics and Information Displays, Institute of Advanced Materials (IAM), Jiangsu National, Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts and Telecommunications, 9 Wenyuan Road, Nanjing, 210023, P.R. China. wei-huang@njtech.edu.cn, iamdirector@fudan.edu.cn.|Key Laboratory of Flexible Electronics (KLOFE), Institute of Advanced Materials (IAM), Jiangsu National, Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University (Nanjing Tech), 30 South Puzhu Road, Nanjing, 211816, P.R. China. wei-huang@njtech.edu.cn, iamdirector@fudan.edu.cn.
Wei
W
Huang
aromaticity; conjugation; fused-ring systems; polycyclic aromatic hydrocarbons; synthesis design