Supporting information for Effect of substituents on the electron transport properties of bay substituted perylene diimide derivatives Sivamurugan Vajiravelu, a Lygaitis Ramunas, b Gražulevičius Juozas Vidas, b Gaidelis Valentas, c Jankauskas Vygintas c and Suresh Valiyaveettil*,a a Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117 543 b Department Organic Technology, Kaunas University of Technology, Radvilenu pl. 19, LT-50254, Kaunas, Lithuania c Department of Solid State Electronics, Vilnius University, Sauletekio al. 9, LT-10222, Vilnius, Lithuania
Figure 1S 1 H NMR of 1,7-dibromo perylene 8.408 8.381 7.702 7.447 7.420 4.721 500 8.408 8.381 7.702 7.447 7.420 100 50 400 0 1.73 1.95 2.00 300 8.50 ppm (f1) 8.00 7.50 200 100 0 2.00 1.95 1.73 ppm (f1) 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0
siva239 *** Current Data Parameters *** 9.4947 9.4673 8.9145 8.7113 8.6855 7.2600 9.4947 9.4673 0.4527 2.0000 0.6994 1.9876 2.0049 0.8657 4.0334 3.9976 33.228 11.181 4.2019 8.9145 8.7113 8.6855 1.7514 1.3931 1.2577 0.8742 0.8518 0.0678 NAME : de02siva EXPNO : 1 PROCNO : 1 *** Acquisition Parameters *** DATE_t : 22:05:11 DATE_d : Dec 01 2007 NS : 24 SFO1 : 300.1318534 MHz SOLVENT : CDCl3 *** Processing Parameters *** AQORDER : 0 *** 1D NMR Plot Parameters *** Start : 10.00 ppm Stop : 0.00 ppm Integral 2.0000 0.6994 1.9876 2.0049 9.5 9.4 9.3 9.2 9.1 9.0 8.9 8.8 8.7 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 Figure 2S 1 H NMR spectrum of 1,7-dibromo-N,N -dodecyl perylene bisimide (PDI)
3000 Intensity (a.u) 1000 500 Intensity (a.u) 2000 1000 885.43 0 1000 1500 2000 2500 3000 m/z 0 800 1000 1200 1400 m/z Figure 3S MALDI-TOF spectrum of 1,7-dibromo-N,N -dodecyl perylene bisimide (PDI)
Figure 4S. 1 H and 13 C NMR of PDI1 siva232 Bruker 8.4099 1.8966 8.4 8.2116 8.1864 Integral 1.8966 2.0743 2.0059 3.9585 4.0000 6.2065 12.407 4.1143 21.355 8.4095 2.0743 8.2 8.4099 8.2116 8.1864 8.0 7.7459 7.7213 7.8 7.2595 7.7459 7.7213 2.0059 6.6804 7.6 7.4 7.2595 7.2 7.0 6.8 6.6804 3.9585 4.2063 3.9817 3.8409 1.7300 1.3947 0.8699 *** Current Data Parameters *** NAME : nv20siva EXPNO : 1 PROCNO : 1 *** Acquisition Parameters *** DATE_t : 05:11:34 DATE_d : Nov 20 2007 DS : 0 NS : 24 O1 : 1853.43 Hz O2 : 1853.43 Hz O3 : 1853.43 Hz SFO1 : 300.1318534 MHz SFO2 : 300.1318534 MHz SFO3 : 300.1318534 MHz SOLVENT : CDCl3 *** Processing Parameters *** AZFW : 0.100 ppm *** 1D NMR Plot Parameters *** SR : 12.05 Hz 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
13 C of PDI1 siva232 Bruker 163.2869 163.0251 154.9157 140.8279 138.9805 137.1914 134.7404 134.1731 131.6930 129.9620 128.9365 128.7911 127.1110 122.0417 121.7072 105.9029 77.4218 77.2036 77.0000 76.5782 61.2467 56.6065 40.8168 31.9074 29.6527 29.6309 29.5655 29.3909 29.3400 28.1400 27.1872 22.6707 14.0812 *** Current Data Parameters *** NAME : nv20siva EXPNO : 2 PROCNO : 1 *** Acquisition Parameters *** DATE_t : 05:14:26 DATE_d : Nov 20 2007 DS : 2 NS : 21016 O1 : 7924.11 Hz O2 : 1200.52 Hz O3 : 7546.30 Hz SFO1 : 75.4756731 MH SFO2 : 300.1312005 MH SFO3 : 75.4752953 MH SOLVENT : CDCl3 *** Processing Parameters *** AZFW : 0.500 ppm *** 1D NMR Plot Parameters *** SR : 1.02 Hz 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
Figure 5S. 1 H and 13 C NMR of PDI2 siva221 *** Current Data Parameters *** 8.6452 Integral 1.0000 1.0191 1.1177 1.1056 0.8590 2.3126 1.3708 2.2483 2.4812 24.084 4.3564 8.6452 8.2612 8.2338 8.0579 8.0437 8.0311 7.5035 7.4898 7.4871 7.3145 7.3063 7.2603 7.2016 7.1896 7.1841 7.1726 8.2612 8.2338 8.0579 8.0437 8.0311 7.5035 7.4898 7.4871 7.3145 7.3063 7.2603 7.2016 7.1896 7.1841 7.1726 4.2021 4.1775 4.1523 4.2021 4.1775 4.1523 1.5670 1.2509 0.8690-0.0010 NAME : oc29siva EXPNO : 2 PROCNO : 1 *** Acquisition Parameters *** BF1 : 300.1300000 MHz DSLIST : SSSSSSSSSSSSSSS EXP : NS : 64 SFO1 : 300.1318534 MHz SOLVENT : CDCl3 Integral 1.0000 8.6 8.4 1.0191 8.2 1.1177 8.0 7.8 7.6 1.1056 7.4 0.8590 2.3126 1.3708 7.2 Integral 4.30 2.2483 4.20 4.10 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
13 C of PDI2 siva221 *** Current Data Parameters *** 135.6394 163.2768 163.2404 133.1884 143.5960 135.6394 133.1884 129.7264 129.6391 128.8464 128.2500 127.4572 122.3152 122.1552 129.7264 129.6391 128.8464 128.2500 127.4572 122.3152 122.1552 40.6539 31.8972 29.6208 29.5990 29.5190 29.3662 29.3153 28.1225 27.1043 22.6533 14.0711 NAME : oc29siva EXPNO : 3 PROCNO : 1 *** Acquisition Parameters *** BF1 : 75.4677490 MHz DSLIST : SSSSSSSSSSSSSSS EXP : NS : 21591 SFO1 : 75.4756731 MHz SOLVENT : CDCl3 136 134 132 130 128 126 124 122 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
Figure 6S. 1 H and 13 C NMR of PDI3 siva226 Bruker 8.6428 8.6428 8.2916 8.2916 7.2600 7.2266 7.2140 7.1488 7.1362 7.0036 6.9916 6.7061 6.6941 Integral 1.7138 2.7556 2.0378 1.7809 1.3231 1.3760 4.0000 3.9622 9.2313 42.360 10.551 4.1800 4.1537 7.2600 7.2266 7.2140 7.1488 7.1362 7.0036 6.9916 2.8366 2.8120 2.7868 6.7061 6.6941 1.6971 1.6725 1.6358 1.3405 1.3191 0.9022 0.8792 0.8671 0.8441 *** Current Data Parameters *** NAME : nv05siva EXPNO : 2 PROCNO : 1 *** Acquisition Parameters *** DATE_t : 03:17:31 DATE_d : Nov 05 2007 NS : 64 SFO1 : 300.1318534 MHz SOLVENT : CDCl3 *** Processing Parameters *** AQORDER : 0 *** 1D NMR Plot Parameters *** Start : 10.00 ppm Stop : 0.00 ppm 1.7138 2.7556 2.0378 1.7809 1.3231 1.3760 8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2 7.0 6.8 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
13 C of PDI3 siva226 *** Current Data Parameters *** 163.2506 146.6172 141.4097 141.1988 135.4386 134.5586 133.8531 133.0094 132.8494 129.7293 129.6056 128.3838 125.0164 124.2600 122.3399 122.1799 77.4218 77.1964 77.0000 76.5782 40.6859 31.9074 31.5583 30.2128 29.6164 29.5364 29.3836 29.3327 28.7291 28.1400 27.1290 22.6707 22.5543 14.0812 14.0521 NAME : nv05siva EXPNO : 3 PROCNO : 1 *** Acquisition Parameters *** DATE_t : 03:20:26 DATE_d : Nov 05 2007 NS : 5244 SFO1 : 75.4756731 MHz SOLVENT : CDCl3 *** Processing Parameters *** AQORDER : 0 *** 1D NMR Plot Parameters *** Start : 200.00 ppm Stop : 0.00 ppm 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
Figure 7S. 1 H and 13 C NMR of PDI4 siva210 *** Current Data Parameters *** 8.7045 8.0591 8.0317 7.8477 7.8263 7.8208 7.8082 7.7995 7.2604 7.2390 7.2045 8.7045 8.0591 8.0317 7.8477 7.8263 7.8208 7.8082 7.7995 Integral 1.9628 2.5393 4.4954 2.2608 3.8588 6.0000 4.2504 39.050 9.1068 4.2023 4.1787 4.1530 4.1234 3.9930 7.2604 7.2390 7.2045 1.7254 1.7030 1.6756 1.5030 1.4258 1.3704 1.3332 1.2844 1.2439 1.0077 0.9760 0.9541 0.8828 0.8735 0.8631 0.8511 0.8396 0.8308 NAME : oc28siva EXPNO : 3 PROCNO : 1 *** Acquisition Parameters *** DATE_t : 00:49:24 DATE_d : Oct 28 2007 NS : 24 SFO1 : 300.1318534 MHz SOLVENT : CDCl3 *** Processing Parameters *** AQORDER : 0 *** 1D NMR Plot Parameters *** Start : 10.00 ppm Stop : 0.00 ppm Integral 1.9628 2.5393 4.4954 2.2608 8.8 8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
13 C of PDI4 siva210 *** Current Data Parameters *** 163.4978 163.4178 158.7049 141.0024 137.2496 135.6786 134.9295 134.4204 132.4858 130.1293 129.9111 129.3511 128.5874 128.0710 127.5619 127.3728 122.3399 121.8672 119.7434 106.0120 77.4218 77.1964 77.0000 76.5709 55.4646 40.6350 31.9001 29.6309 29.6091 29.5364 29.3909 29.3255 28.1545 27.1363 22.6634 14.0740 NAME : oc28siva EXPNO : 6 PROCNO : 1 *** Acquisition Parameters *** DATE_t : 03:41:49 DATE_d : Oct 28 2007 NS : 26014 SFO1 : 75.4756731 MHz SOLVENT : CDCl3 *** Processing Parameters *** AQORDER : 0 *** 1D NMR Plot Parameters *** Start : 200.00 ppm Stop : 0.00 ppm 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
Figure 8S. 1 H and 13 C NMR of PDI5 siva213 *** Current Data Parameters *** 8.6565 8.6565 7.8281 7.8046 7.7569 7.7322 7.7070 7.6857 7.6610 7.3761 7.3559 7.3334 7.2600 7.8281 7.8046 7.7569 7.7322 7.7070 7.6857 7.6610 7.0140 6.9910 6.9636 6.6168 6.5927 6.5670 6.1566 6.1314 Integral 2.3256 2.1200 6.4745 4.3489 2.1523 2.1125 1.8403 0.5156 4.0000 4.9286 43.746 7.8118 7.3761 7.3559 7.3334 7.2600 5.7446 7.0140 6.9910 6.9636 4.1378 1.7322 1.4139 0.8715 NAME : oc28siva EXPNO : 4 PROCNO : 1 *** Acquisition Parameters *** DATE_t : 00:55:24 DATE_d : Oct 28 2007 NS : 24 SFO1 : 300.1318534 MHz SOLVENT : CDCl3 *** Processing Parameters *** AQORDER : 0 *** 1D NMR Plot Parameters *** Start : 10.00 ppm Stop : 0.00 ppm Integral 2.3256 2.1200 6.4745 4.3489 2.1523 2.1125 1.8403 0.5156 6.6168 6.5927 6.5670 6.1566 6.1314 5.7446 8.8 8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2 7.0 6.8 6.6 6.4 6.2 6.0 5.8 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
13 C of PDI5 siva213 *** Current Data Parameters *** 163.2914 162.9059 141.6833 139.7559 137.7413 135.0212 134.5703 134.3448 132.4538 129.7992 129.5519 129.4501 129.2537 128.5991 128.0828 128.0173 127.7337 127.6464 127.3482 126.6063 122.7735 121.9953 77.4263 77.2008 77.0044 76.5753 76.2262 40.5231 31.9118 29.6281 29.5845 29.4245 29.3372 28.2244 27.1844 22.6751 14.0930 NAME : oc28siva EXPNO : 5 PROCNO : 1 *** Acquisition Parameters *** DATE_t : 00:58:56 DATE_d : Oct 28 2007 NS : 6648 SFO1 : 75.4756731 MHz SOLVENT : CDCl3 *** Processing Parameters *** AQORDER : 0 *** 1D NMR Plot Parameters *** Start : 200.01 ppm Stop : 0.01 ppm 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10
8000 Intensity / a.u 6000 4000 2000 1058.72 PDI1 0 1000 1500 2000 2500 3000 3500 4000 MALDI-TOF of PDI1 m/z
10000 8000 1038.75 PDI4 Intensity / a.u 6000 4000 2000 0 1000 1500 2000 2500 3000 3500 4000 m / Z MALDI-TOF of PDI4
500 1225.67 m/z PDI3 400 Intensity (a.u) 300 200 100 0 500 1000 1500 2000 2500 3000 3500 m/z MALDI-TOF of PDI3
Absorbance (a.u) 3.0 2.5 2.0 1.5 1.0 0.5 Solution state PDI PDI1 PDI2 PDI3 PDI4 PDI5 0.0 300 400 500 600 700 800 Wavelength (nm) Figure 9S. Absorption spectra in solution
Figure 10S. Absorption spectra of thin films Absorbance (a.u) 1.0 Spin coated thin film 0.8 0.6 0.4 0.2 0.0 PDI1 PDI2 PDI3 PDI4 PDI5 300 400 500 600 700 800 900 Wavelength (nm)
Figure 11S. Emission spectra in solution Emission (a.u) 100 80 60 40 20 0 PDI PDI1 PDI2 PDI4 PDI3 PDI5 500 600 700 800 Wavelength (nm)
Figure 12S. DSC curves of PDI1. Heating-cooling-heating curve. Recorded under nitrogen atmosphere Heat Flow < endo exo > PDI1 Tg 1 st cooling 1 st heating 2 nd heating Tm 50 100 150 200 250 300 Temperature [ o C]
Figure 13S. DSC curves of PDI3. Heating-cooling-heating curve. Recorded under nitrogen atmosphere Heat Flow < endo egzo > PDI3 Tg Tm 1 st cooling 1 st heating 2 nd heating 50 100 150 200 250 300 Temperature [ o C]
Figure 14S. DSC curves of PDI4. Heating-cooling-heating curve. Recorded under nitrogen atmosphere Heat Flow < endo egzo > 2 nd heating 1 st heating 1 st cooling PDI4 50 100 150 200 250 300 Temperature [ o C]
Figure 15S. XTOF transients for blend of PDI4and PC-Z. Arrow marks in insert indicates a transit time of holes 10 2 8J69, Al+[PDI4+(PC-Z), 3:1], d=5μm t =25 o C du/dt (a.u.) 10 1 10 0 10-1 10-2 du/dt (a.u.) 8 6 4 2-336 V U 0 : -492 V Pakaitinus 5 min. -472 V -452 V -404 V -396 V -336 V -300 V -224 V -104 V UV flash 10-3 0.0000 0.0001 0.0002 0.0003 t (s) 10-6 10-5 10-4 10-3 t (s)
Figure 16S. XTOF transients for blend of PDI5and PC-Z. Arrow marks in insert indicates a transit time of holes 10 0 8J70, Al+[PDI5+(PC-Z), 3:1], d=6μm t =25 o C U 0 : 10-1 du/dt (a.u.) 10-2 10-3 du/dt (a.u.) 0.2 0.1-870 V -1120 V -990 V -870 V -740 V -628 V -584 V UV flash 10-4 0.0 0.00 0.01 0.02 0.03 t (s) 10-4 10-3 10-2 10-1 t (s)