ACCEPTED MANUSCRIPT
THF): δ(ppm) 8.21-8.18(d, 1H), 8.08(s, 1H), 7.92-7.89(d, 1H), 7.47-7.41(t, 1H), 7.37-7.32(t, 1H), 7.23-7.19(t,
3H), 7.13-7.08(m, 1H), 6.99-6.88(m, 3H), 6.76-6.73(d, 1H), 2.48(s, 6H). 13C-NMR (75 MHz, CDCl3): δ= 148.91,
148.13, 143.63, 134.17, 132.99, 132.21, 132.15, 131.98, 129.58, 127.19, 127.02, 126.73, 126.55, 126.00,
125.74, 125.22, 124.53, 124.28, 123.78, 117.72, 19.14; LRMS(EI, m/z): [M+] calc’d. for C46H38N2, 618.30;
found, 618; Elemental analysis calc’d. (%) for C46H38N2: C 89.28, H 6.19, N 4.53; found: C 87.28, H 6.26, N
4.17%.
Tetra-m-tolylchrysene-6,12-diamine
(m-DPAC).
Di-o-tolyl-amine
1.33g
(6.77
mmol),
6,12-
dibromochrysene 1.0g (2.60 mmol), Pd(OAc)2 0.07g (0.312 mmol), sodium tert-butoxide 1.5g (15.6 mmol),
and tri-tert-butylphosphine 0.37mL (0.313 mmol) were added to 100 mL of anhydrous toluene in a 3-neck
round bottom flask under a N2 atmosphere. The mixture was refluxed at 110 ℃ for 10 h. After the
reaction was finished, the mixture was extracted with chloroform and DI water. The organic layer was
dried with anhydrous MgSO4 and filtered. The solvent was evaporated. The crude product was purified by
column chromatography on silica gel using toluene: hexane = 1 : 3. (0.8g, Yield 50%) 1H NMR (300 MHz,
THF): δ(ppm) 8.63-8.60(m, 2H), 8.14-8.11(d, 1H), 7.58-7.52(t, 1H), 7.47-7.42(t, 1H), 7.09-7.04(t, 2H), 6.97(s,
2H), 6.92-6.89(d, 2H), 6.76-6.73(d, 2H), 2.18(s, 6H). 13C-NMR (75 MHz, CDCl3): δ= 148.88, 143.07, 139.43,
132.27, 131.15, 129.35, 128.21, 127.35, 127.19, 125.53, 124.08, 122.99, 119.61, 21.80; LRMS(EI, m/z): [M+]
calc’d for C46H38N2, 618.30; found, 618; Elemental analysis calc’d (%) for C46H38N2: C 89.28, H 6.19, N 4.53;
found: C 88.41, H 6.27, N 4.21%.
Tetra-p-tolylchrysene-6,12-diamine
(p-DPAC).
Di-o-tolyl-amine
1.33g
(6.77
mmol),
6,12-
dibromochrysene 1.0g (2.60 mmol), Pd(OAc)2 0.07g (0.312 mmol), sodium tert-butoxide 1.5g (15.6 mmol)
and tri-tert-butylphosphine 0.37mL (0.313 mmol) were added to 100 mL of anhydrous toluene in a 3-neck
round bottom flask under a N2 atmosphere. The mixture was refluxed at 110 ℃ for 10 h. After the
reaction was finished, the mixture was extracted with chloroform and DI water. The organic layer was
dried with anhydrous MgSO4 and filtered. The solvent was evaporated. The crude product was purified by
column chromatography on silica gel using toluene: hexane = 1 : 5. (0.44g, Yield 25%) 1H NMR (300 MHz,
THF): δ(ppm) 8.58-8.55(m, 2H), 8.11-8.08(d, 1H), 7.56-7.51(t, 1H), 7.44-7.39(t, 1H), 6.99(s, 8H), 2.25(s, 6H).
13C-NMR (75 MHz, CDCl3): δ= 146.68, 143.21, 132.23, 131.47, 131.01, 130.16, 128.02, 127.21, 127.11,
125.51, 124.04, 122.50, 122.29, 20.97; LRMS(EI, m/z): [M+] calc’d for C46H38N2, 618.30; found, 618; Elemental
analysis calc’d (%) for C46H38N2: C 89.28, H 6.19, N 4.53; found: C 88.49, H 5.96, N 4.07%.
2.2. Materials, Measurements, and OLED Fabrication
Reactant di-p-tolylamine and 3,3'-dimethyldiphenylamine were purchased from Sigma-Aldrich and Alfa -
Aesar. Reagents and solvents were purchased as reagent grade and were used without further purification.