N-heteroquinones: quadruple weak hydrogen bonds and n-channel transistors
Qin Tang, Zhixiong Liang, Jing Liu, Jianbin Xu, Qian Miao
Synthesis General: The reagents and starting materials employed were all commercially available and were used without any further purification. 1 H-NMR or 13 C-NMR spectra were recorded on a Brucker ADVANCE III 400MHz spectrometer. Mass spectra were recorded on a Therno Finnigan MAT 95 XL spectrometer. Differential scanning calorimetry was carried on Perkin Elmer Differential Scanning Calorimeter 6. X-ray crystallography was carried on Bruker AXS Kappa ApexII Duo Diffractometer.
... ,12,14-tetraazapentacene and 5,12-dihydro-5,12-diazatetracene were prepared by following the reported procedures. 1, 2 TAPQ and DATQ were prepared by modifying the reported procedures. 3 Scheme S-1. To a solution of 25ml of H 2 SO 4 in 100mL water was added 808mg (2.84 mmol) of 5,14-dihydro-5,7,12,14-tetraazapentacene, 1 and then 4g (13.6mmol) of potassium dichromate slowly. The resulting mixture was refluxed for 1 hour and then poured into 200mL of ice-water. The resulting yellow powder was filtered and washed with water and acetone subsequently. 813mg of TAPQ was collected in a yield of 92% after drying under vacuum. No peak was found up to 450°C in DSC for melting or decomposition. 1 H-NMR (DMSO-d 6 ) δ (ppm): 8.48 (dd, J 1 =3.2Hz, J 2 =6.4Hz, 4H), 8.18 (dd, J 1 =3.2Hz, J 2 =6.4Hz, 4H); 13 C-NMR was not taken due to the low solubility; HRMS (EI+): cald. For ([M]+): 312.0642, found: 312.0649. 6,11-diaza-5,12-tetracenequinone (DATQ) Potassium dichromate (1g) was added slowly into a warm solution of 5,12-dihydro-5,12-diazatetracene 2 (232mg, 1mmol) in 30mL of acetic acid. The solution was then refluxed for 1 hour. After the reaction mixture was cooled down, DATQ was collected as yellow crystals (222mg, 85%) by filtration and wash with acetone. mp: 320°C with decomposition. 1 H-NMR (CDCl 3 ) δ (ppm): 8.53 (dd, J 1 =3.2Hz, J 2 =6.4Hz, 2H), 8.51 (dd, J 1 =3.2Hz, J 2 =6.4Hz, 2H), 8.05 (dd, J 1 =3.2Hz, J 2 =6.4Hz, 2H), 7.94 (dd, J 1 =3.2Hz, J 2 =6.4Hz, 2H); 13 C-NMR (CDCl 3 ) δ (ppm): 180.273, 143.315, 143.224, 134.417, 132.979, 130.283, 127.482; HRMS (EI+): cald. For ([M]+): 260.0580, found: 260.0574.