Chlorination: A general route towards electron transport in organic semiconductors.

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1 Tang et al, S1 Chlorination: A general route towards electron transport in organic semiconductors. Ming Lee Tang, Joon Hak Oh Anna Devi Reichardt and Zhenan Bao *. Department of Chemistry and Chemical Engineering, Stanford University, 381 North-South Mall, Stanford, California *zbao@stanford.edu RECEIVED DATE Synthesis. Chemical reagents were purchased from Aldrich Chemical Co, TCI America, Lancaster, or Alfa Aesar and were used as received, except for 2,2,2-trifluoroethanol that was dried with calcium sulphate and trimethylsilylchloride that was distilled over sodium. Trialkylsilylacetylenes were purchased from GFS and used as received. 1,2,3,4-tetrachloro-5,8-dihydroxyanthraquinone (2): To a 100ml flame-dried round bottom flask with a NaOH trap for HCl was added 13.33g (90.88mmol) 1-ethyl-3-methylimidazolium chloride 1, followed by 24.25g (181.75mmol) aluminium chloride. The mixture was stirred and heated to 100 C until everything dissolved. An intimate mixture of 1, 3,4,5,6-tetrachlorophthalic anhydride (6.50g, 22.72mmol) and 1,4-dihydroxybenzene (2.82g, 25.56mmol) was added in small portions over two hours to the above melt, after which 12.13g (90.88mmol) of AlCl 3 was added. The temperature was raised to 180 C and maintained for 12hrs. The hot mixture was cooled to room temperature and quenched with 500ml 3M HCl (aq), filtered, then washed copiously with DI water and dried over P 2 O 5 with house vacuum. A dull orange powder was collected (7.73g, 90%.) 1 H NMR (CDCl 3, 500MHz): δ H (s, 2 H), 7.36 (s, 2 H) ppm. MS (+DEI/ APCI) m/z: 378 (M + ) 6,7,8,9-tetrachloro-1,4-anthraquinone (3): Under Ar(g), 4.03g (106.55mmol) of NaBH 4 was added in small portions 2 over an hour a stirred solution of 1,2,3,4-tetrachloro-5,8-dihydroxyanthraquinone (7.50g, 19.84mmol) in 186ml anhydrous methanol in an ice bath. The flask was refluxed for 16 hrs. The hot mixture was cooled to room temperature and quenched with 200ml 3.0M HCl (aq) and filtered. The residue was washed with DI water and dried over P 2 O 5 with house vacuum. An orange powder was collected (6.62g, 96%.) 1 H NMR (CDCl 3, 500MHz): δ H 9.05 (s, 2 H), 7.16 (s, 2 H) ppm. MS (+DEI/ APCI) m/z: 346 (M + ) 6,7,8,9-tetrachloro-1,4dihydroxyanthraquinone (4): To a solution of 6,7,8,9-tetrachloro-1,4- anthraquinone (3.3g, 9.57mmol) in 383ml of dioxane was added 63.29g (0.363mol) of Na 2 S 2 O 4 dissolved in 383ml of DI water. The orange suspension turns into a darker reddish suspension as it was stirred overnight. The reaction mixture was quenched with water, filtered and washed with DI water. The brown solid was dried with a pump to give a yield of 3.0g or 90%. 1 H NMR (CDCl 3, 500MHz): δ H 9.07 (s, 2 H), 6.81 (s, 2 H) ppm. MS (+DEI/ APCI) m/z: 348 (M + ) (5,6,7,8-tetrachloro-1,4-dihydroanthracene-1,4-diyl)bis(oxy)bis(trimethylsilane) (5): To a flame-dried Schlenk tube was added 0.10g (0.287mmol) of 6,7,8,9-tetrachloro-1,4dihydroxyanthraquinone, 0.72ml dry acetonitrile, and ml (0.632mmol) trimethylsilylchloride 3. Hexamethyldisilazane (0.132ml, 0.632mmol) was then added dropwise. The reaction was stirred at room temperature overnight, quenched with distilled water and extracted with dichoromethane. The organic extract was washed with saturated sodium bicarbonate, dried with magnesium sulfate and the solvent removed under reduced 1

2 Tang et al, S2 pressure, yielding a dark brown powder (95mg, 67%.) 1 H NMR (CDCl 3, 500MHz): δ H 9.07 (s, 2 H), 6.81 (s, 2 H), 0.38 (s, 18 H) ppm. 13 C NMR (CDCl 3, 500MHz): δ C , , , , , , , 0.55 ppm. MS (+DEI) m/z: 492 (M + ) 7,8,9,10-tetrachloro-tetraceno[2,3-b]thiophene-5,12-dione 4 (6): (5,6,7,8-tetrachloro-1,4-dihydroanthracene-1,4-diyl)bis(oxy)bis(trimethylsilane) (0.609g, 1.24mmol), 2,3-thiophenedicarbaldehyde (0.173g, 1.24mmol), tris(pentafluorophenyl)boron (25.3mg, 0.050mmol), and 6.9ml of dry dichloromethane were added to a flame-dried round bottom flask under argon. Tetrabutylammonium fluoride (1.0M in THF, 2.47ml, 2.47mmol) was added dropwise to the reaction mixture, which was then stirred overnight at room temperature. Later, 5ml of dry 2,2,2-trifluoroethanol was added to the mixture, and allowed to reflux for four hours. The suspension was cooled to room temperature, quenched with water, filtered and the residue washed with ethanol, yielding a yellow powder (0.32g, 57%). This compound is very insoluble, such that even proton NMR could not be measured at 90 C in DMSO. MS (+ve DEI) m/z: 452 (M + ) 7,8,9,10-tetrachloro-5,12-bis(triisopropylsilylethynyl)tetraceno[2,3-b]thiophene (TIPSEthiotetCl 4 ): nbuli was added dropwise (1.89 ml, 3.02 mmol) to triisopropylsilylacetylene (0.57 g, 3.13 mmol), followed by dry ether (50.4 ml). The mixture was heated to 60 C for 30 mins, after which 7,8,9,10- tetrachloro-tetraceno[2,3-b]thiophene-5,12-dione (0.23 g, mmol) was added. The mixture was stirred at 60 C overnight, then SnCl 2.2H 2 O (0.736 g, 3.26 mmol) dissolved in 1.4ml of 10% HCl(aq) was added, and the reaction mixture heated for an hour at 60 C. The mixture was then quenched with water, extracted with dichloromethane, washed with brine, dried with MgSO 4, and the solvent removed under reduced pressure. This crude product was then run through a hexane silica gel column. A purple powder was collected (0.20 g, yield 51 %). This powder was recrystallized in degassed hexanes twice to give crystalline purple needles. 1 H NMR (CDCl 3, 500MHz): δ H 9.76 (s, 2 H), 9.21 (s, 1 H), 9.17 (s, 1 H), 7.61 (d, J = 5.5 Hz, 1 H), 7.44 (d, J = 5.5 Hz, 1 H), 1.35 (s, 36H), 1.33 (s, 6H) ppm. 13 C NMR (CDCl 3, 500MHz): δ C , , , , , , , , , , , , , , , , , , , , , , , , 19.19, ppm. HRMS calcd for C 42 H 49 Si 2 SCl 4 (MH + ) ; found: ,2,3,4-tetrachloro-pentacene-6,13-dione (7): To a flame-dried rbf, was added 3.76g of α,α,α,α - tetrabromo-o-xylene (8.92mmol), 6,7,8,9-tetrachloro-1,4-anthraquinone (3.10g, 8.96mmol) in 32ml of dry DMF. The solution was bubbled for 25 mins with Ar(g), after which 8.92g (59.51mmol) of NaI was added. The reaction mixture was stirred at 60 C for 1 day, then cooled to room temperature, quenched with 200ml DI water and filtered. The residue was washed with MeOH and EtOH, then stirred with 50ml of chloroform for 30 mins. This suspension was filtered again to give a yellow-brown solid (1.72g, 43%). HRMS calcd for C 22 H 9 O 2 Cl 4 (MH + ) ; found: ,2,3,4-tetrachloro-6,13-bis-(triisopropylsilylethynyl) pentacene (TIPSEpentCl 4 ): This molecule was synthesized as TIPSEthiotetCl 4 above to give a purple powder in 20% yield. 1 H NMR (CDCl 3, 500MHz): δ H 9.75 (s, 2 H), 9.33 (s, 2 H), 7.99 (m, 2 H), 7.47 (m, 2 H), 1.37 (s, 36H), 1.36 (s, 6H) ppm. 13 C NMR (CDCl 3, 500MHz): δ C , , , , , , , , , , , , , 19.21, ppm. HRMS calcd for C 44 H 50 Si 2 Cl 4 (M + ) ; found:

3 Tang et al, S3 Figure S1. Out-of-plane X-ray diffraction for TIPSEthiotetCl4 on different substrate surfaces and temperatures. Figure S2. Out-of-plane X-ray diffraction for TIPSEpentCl 4 on different substrate surfaces and temperatures. 3

4 Tang et al, S4 Figure S3. Out-of-plane X-ray diffraction for TIPSEpentF 4 on different substrate surfaces and temperatures. Figure S4. Out-of-plane X-ray diffraction for TIPSEpentF 8 on different substrate surfaces and temperatures. 4

5 Tang et al, S5 Figure S5. 1x1µm AFM images of TIPSEpentCl 4 at a substrate temperate of RT (left), 60 C (right); on OTS/SiO 2 /Si (top) and on SiO 2 /Si (bottom). 5

6 Tang et al, S6 30 nm 35 nm 200nm 200nm 25 nm 20 nm 200nm 200nm Figure S6. AFM images of TIPSEpentF 4 at a substrate temperate of RT (left), 60 C (right); on OTS/SiO 2 /Si (top) and on SiO 2 /Si (bottom). 30 nm 35 nm 400nm 400nm 120 nm 75 nm 200nm 200nm Figure S7. AFM images of TIPSEpentF 8 at a substrate temperate of RT (left), 60 C (middle); 80 C (right); on OTS/SiO 2 /Si (top) and on SiO 2 /Si (bottom). 6

7 Tang et al, S7 50nm 35nm 45nm 200nm 200nm 400nm 200nm 90nm 400nm 20nm 400nm 70nm Figure S8. Typical transfer (left) and output (right) curves of TIPSEpentCl 4, on OTS treated SiO 2, for devices grown at a substrate temperature, T D of 60ºC, L=100µm, W/L=20. Solid lines refer to drain current vs. gate voltage (y-axis on left), while the open circles refer to the square root of the drain current vs. gate voltage (y-axis on right). Figure S9. Typical transfer (left) and output (right) curves of TIPSEpentF 4, on OTS treated SiO 2, for devices grown at a substrate temperature, T D of RT, L=100µm, W/L=20. Solid lines refer to drain 7

8 Tang et al, S8 current vs. gate voltage (y-axis on left), while the open circles refer to the square root of the drain current vs. gate voltage (y-axis on right). Figure S10. Typical transfer (left) and output (right) curves of TIPSEpentF 8, on OTS treated SiO 2, for devices grown at a substrate temperature, T D of 60ºC, L=100µm, W/L=20. Solid lines refer to drain current vs. gate voltage (y-axis on left), while the open circles refer to the square root of the drain current vs. gate voltage (y-axis on right). 8

9 Tang et al, S9 Figure S11. Typical transfer (left) and output (right) curves of Cl 16 CuPc, on OTS treated SiO 2, for devices grown at a substrate temperature, T D of 200ºC, L=100µm, W/L=20. Figure S12. UV-Vis of 45nm thin films of F 16 CuPc and Cl 16 CuPc on quartz (left), with the long wavelength absorption maxima expanded (right). 9

Tang et al, S10 Figure S13. DFT calculations with B3LYP/6-31G+d for the ground state of TIPSEthiotetCl 4, TIPSEthiotetF 4, TIPSEpentCl 4, TIPSEpentF 4 with the HOMO and LUMOs illustrated. Table S1.

10 Tang et al, S10 Figure S13. DFT calculations with B3LYP/6-31G+d for the ground state of TIPSEthiotetCl 4, TIPSEthiotetF 4, TIPSEpentCl 4, TIPSEpentF 4 with the HOMO and LUMOs illustrated. Table S1. A summary of the average p-channel OFET mobilities (except for Cl 16 CuPc, n-channel in air), µ, and their standard deviations, with the on/off ratios of the source-drain current and threshold voltages, V T, on 45nm top contact devices with gold electrodes on both OTS treated and bare SiO 2 surfaces, W/L =20, L=100µm, measured in air. Note, no n-channel behavior was observed for these acene derivatives in air. MOLECULE TIPSEthiotetCl 4 TIPSEpentCl 4 T D / ºC RT RT SiO 2 /Si OTS/SiO 2 /Si µ (cm 2 /Vs) ±0.02 on/off No TFT 4E+04 V T (V) +15 µ (cm 2 /Vs) (3.09 ±1)E ±0.03 on/off 2E+04 8E+06 V T (V) µ (cm 2 /Vs) (6.10 ±2)E ±0.03 on/off 2E+06 9E+05 V T (V) µ (cm 2 /Vs) (2.45 ±0.7)E ±0.006 on/off 1E+06 2E+06 V T (V) µ (cm 2 /Vs) ± ±

11 Tang et al, S11 60 RT TIPSEpentF 4 60 RT TIPSEpentF Cl 16 CuPc 200 on/off 2E+05 3E+06 V T (V) µ (cm 2 /Vs) (3.48 ±1)E ±0.01 on/off 6E+03 3E+06 V T (V) µ (cm 2 /Vs) (1.61 ±0.3)E ±0.002 on/off 1E+05 1E+06 V T (V) µ (cm 2 /Vs) (1.09±0.09)E ±0.01 on/off 3E+03 2E+07 V T (V) µ (cm 2 /Vs) ±0.05 on/off No TFT 7E+06 V T (V) +20 µ (cm 2 /Vs) ± ±0.01 on/off 1E+04 3E+05 V T (V) µ (cm 2 /Vs) (6.8 ± 0.7) E ±0.02 on/off 1E+06 1E+07 V T (V) +(18~32) +(10~27) Table S2: The Z-matrix of optimized 4,5,6,7-tetrafluorobenzo[b]thiophene that has a HF energy of a.u according to B3LYP/6-31G+d calculations with Gaussian03. C C,1,B1 C,2,B2,1,A1 C,3,B3,2,A2,1,D1,0 C,4,B4,3,A3,2,D2,0 C,5,B5,4,A4,3,D3,0 S,4,B6,3,A5,2,D4,0 C,3,B7,2,A6,1,D5,0 C,8,B8,3,A7,2,D6,0 H,8,B9,3,A8,2,D7,0 F,5,B10,4,A9,3,D8,0 F,6,B11,5,A10,4,D9,0 F,1,B12,2,A11,3,D10,0 F,2,B13,1,A12,6,D11,0 H,9,B14,8,A13,3,D12,0 Variables: B1= B2= B3= B4= B5= B6=

12 Tang et al, S12 B7= B8= B9= B10= B11= B12= B13= B14= A1= A2= A3= A4= A5= A6= A7= A8= A9= A10= A11= A12= A13= D1= D2= D3= D4= D5= D6= D7= D8= D9= D10= D11= D12= Table S3: The Z-matrix of optimized 4,5,6,7-tetrachlorobenzo[b]thiophene that has a HF energy of a.u according to B3LYP/6-31G+d calculations with Gaussian03. C C,1,B1 C,2,B2,1,A1 C,3,B3,2,A2,1,D1,0 C,4,B4,3,A3,2,D2,0 C,5,B5,4,A4,3,D3,0 S,4,B6,3,A5,2,D4,0 C,3,B7,2,A6,1,D5,0 C,8,B8,3,A7,2,D6,0 H,8,B9,3,A8,2,D7,0 H,9,B10,8,A9,3,D8,0 12

13 Tang et al, S13 Cl,2,B11,1,A10,6,D9,0 Cl,1,B12,2,A11,3,D10,0 Cl,6,B13,5,A12,4,D11,0 Cl,5,B14,4,A13,3,D12,0 Variables: B1= B2= B3= B4= B5= B6= B7= B8= B9= B10= B11= B12= B13= B14= A1= A2= A3= A4= A5= A6= A7= A8= A9= A10= A11= A12= A13= D1= D2= D3= D4= D5= D6= D7= D8= D9= D10= D11= D12= Table S4: Cartesian coordinates of optimized TIPSEthiotetF 4 that has a HF energy of a.u according to B3LYP/6-31G+d calculations with Gaussian03. C C

14 C C C C C C C C C H C C C H H H S C C H H C C C C F F F F C C C C C H H H C H H H Tang et al, S14 Table S5: Cartesian coordinates of optimized TIPSEthiotetCl 4 that has a HF energy of HF= a.u according to B3LYP/6-31G+d calculations with Gaussian03. C C C C C

15 C C C C C C H C C C H H H S C C H H C C C C C C C C C H H H C H H H Cl Cl Cl Cl Tang et al, S15 Table S6: Cartesian coordinates of optimized TIPSEpentF 4 that has a HF energy of a.u according to B3LYP/6-31G+d calculations with Gaussian03. C C C C C C H H

16 H H C C C C C C C C C H C H C C C C H H C C C C C C C H H H C H H H F F F F Tang et al, S16 Table S7: Cartesian coordinates of optimized TIPSEpentCl 4 that has a HF energy of a.u according to B3LYP/6-31G+d calculations with Gaussian03. C C C C C C H H

17 H H C C C C C C C C C H C H C C C C H H C C C C C C C H H H C H H H Cl Cl Cl Cl Tang et al, S17 Table S8: Cartesian coordinates of optimized TIPSEpentF 8 that has a HF energy of a.u according to B3LYP/6-31G+d calculations with Gaussian03. C C C C C C C C

18 C C C C C C C H C H C C C C H H C C C C C C C H H H C H H H F F F F F F F F Tang et al, S18 Table S9: Cartesian coordinates of optimized TIPSEpentCl 8 that has a HF energy of a.u according to B3LYP/6-31G+d calculations with Gaussian03. C C C C C C C C

19 C C C C C C C H C H C C C C H H C C C C C C C H H H C H H H Cl Cl Cl Cl Cl Cl Cl Cl Tang et al, S19 References: (1) Boon, J. A.; Levisky, J. A.; Pflug, J. L.; Wilkes, J. S. Journal of Organic Chemistry 1986, 51, (2) Chen, Z. H.; Swager, T. M. Organic Letters 2007, 9, (3) Willis, J. P.; Gogins, K. A. Z.; Miller, L. L. Journal of Organic Chemistry 1981, 46, Complete citation for Ref. 33: 19

20 Tang et al, S20 Frisch, M. J. T., G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; and Pople, J. A.; Gaussian Inc: Wallingford, CT.,

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