Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006
Twisting of Conjugated Oligomers and Polymers: Case Study of Oligo- and Polythiophene Sanjio S. Zade and Michael Bendikov* Department of Organic Chemistry, Weizmann Institute of Science, 76100 Rehovot, Israel Tel: +972-8-9346028; Fax: +972-8-9344142 E-mail: michael.bendikov@weizmann.ac.il S1
Twist angle 0 View 1 View 2 2 4 6 S2
8 Figure 1 cont. S3
10 12 14 16 18 S4
Figure 1 cont. S5
20 22 24 26 28 S6
Figure 1 cont. S7
30 32 34 36 Figure S1: Two views of optimized sexithiophene each for increment of 2 interring torsion angle S8
Figure S2: PBC (B3LYP/6-31G*) optimized unit cell (24 monomers) of the polymer with 15 interring twist angle (Spiral Conformation) Figure S3: PBC (B3LYP/6-31G*) optimized unit cell (12 monomers) of the polymer with 30 interring twist angle (Spiral Conformation) S9
Figure S4: PBC (B3LYP/6-31G*) optimized unit cell (6 monomers) of the polymer with 60 interring twist angle (Spiral Conformation) S10
Figure S5: PBC (B3LYP/6-31G*) optimized unit cell (4 monomers) of the polymer with 90 interring twist angle (Spiral Conformation) Figure S6: PBC (B3LYP/6-31G*) optimized unit cell of the polymer with 30 interring twist angle (updown Conformation) [2 monomer has taken as a unit cell] Figure S7: PBC (B3LYP/6-31G*) optimized unit cell of the polymer with 60 interring twist angle (updown Conformation) [2 monomer has taken as a unit cell] S11
Figure S8: PBC (B3LYP/6-31G*) optimized unit cell of the polymer with 90 interring twist angle (updown Conformation) [2 monomer has taken as a unit cell] Figure S9: PBC (B3LYP/6-31G*) optimized unit cell of the poly(3-methylthiophene) [2 monomer has taken as a unit cell] Figure S10: PBC (B3LYP/6-31G*) optimized unit cell of the poly(3,4-methylthiophene) [2 monomer has taken as a unit cell] (Interring bond angle: 68 ) S12
Figure S11: PBC (B3LYP/6-31G*) optimized unit cell of the poly(3,4-methylthiophene) [5 monomer has taken as a unit cell] (Interring bond angle: ~33 ) Figure S12: PBC (B3LYP/6-31G*) optimized unit cell of the polythiophene having 3,4-dimethyl groups on alternate thiophene ring [2 monomer has taken as a unit cell] (Interring bond angle: ~40 ) Figure S13: PBC (B3LYP/6-31G*) Optimized unit cell of the polythiophene having 3,4-diethyl groups on alternate thiophene ring [2 monomer has taken as a unit cell] (Interring bond angle: ~45 ) S13
Figure S14: PBC (B3LYP/6-31G*) Optimized unit cell of the polythiophene having 3,4-dibutyl groups on alternate thiophene ring [2 monomer has taken as a unit cell] (Interring bond angle: ~46 ) Figure S14: PBC (B3LYP/6-31G*) Optimized unit cell of the polycyclopenta[c]thiophene S14
6.1 6T 6.0 IP (ev) 5.9 5.8 5.7 0 5 10 15 20 25 30 35 40 Figure S15. Change in IP values for the sexithiophene with twist angle S15
Tables for Relative Energies, Difference in Energies, Frontier Orbital Energies and Band Gaps Table S1. 6T Interring Relative Energy E (kcalmol -1 ) B3LYP/6-31G* 0-3312.077399 2-3312.07745-0.032 4-3312.077473-0.046 6-3312.07746-0.038 8-3312.07741-0.007 10-3312.077333 0.041 12-3312.077251 0.093 14-3312.077167 0.145 16-3312.077067 0.208 18-3312.076938 0.289 20-3312.076761 0.400 22-3312.076523 0.550 24-3312.076232 0.733 26-3312.075893 0.945 28-3312.075496 1.194 30-3312.075036 1.483 32-3312.074547 1.789 34-3312.073945 2.168 36-3312.073374 2.526 Table S2. 6T-updown Interring Relative Energy E (kcalmol -1 ) B3LYP/6-31G* 0-3312.0773098 15-3312.0773986-0.06 30-3312.0760081 0.82 45-3312.0711052 3.89 S16
60-3312.0630408 8.95 Table S3. 15T Interring Relative Energy E (kcalmol -1 ) B3LYP/6-31G* 0-8278.4145810 6.4-8278.4145142 0.04 12.9-8278.4137743 0.51 15-8278.4132662 0.83 30-8278.4065980 5.01 45-8278.3899024 15.49 Table S4. 6T Interring HOMO LUMO Gap 0-4.79686-2.18128 2.62 6-4.80856-2.1701 2.70 12-4.83577-2.14591 2.69 18-4.89129-2.09475 2.80 24-4.96557-2.02427 2.94 30-5.05619-1.93774 3.12 36-5.1517-1.84685 3.30 Table S5. 6T-updown Interring HOMO (ev) LUMO (ev) Gap (ev) 0-4.79686-2.18128 2.62 15-4.84067-2.12985 2.71 30-4.95496-2.00060 2.95 45-5.12775-1.82100 3.31 60-5.38082-1.58752 3.79 Table S6. 15T S17
Interring HOMO (ev) LUMO (ev) Gap (ev) 0-4.64284-2.46428 2.18 6.4-4.66924-2.43653 2.23 12.9-4.70026-2.41258 2.29 15-4.73754-2.37612 2.36 30-4.98299-2.13992 2.84 45-5.32068-1.81066 3.51 Table S7. 6T-Radical Cation Interring Relative Energy E (kcalmol -1 ) B3LYP/6-31G* 0-3311.866719 2-3311.866699 0.01 4-3311.866568 0.09 6-3311.866359 0.23 8-3311.866062 0.41 10-3311.865668 0.66 12-3311.865176 0.97 14-3311.864572 1.35 16-3311.86385 1.80 18-3311.863017 2.32 20-3311.86207 2.92 22-3311.860992 3.59 24-3311.859782 4.35 26-3311.858446 5.19 28-3311.856988 6.11 30-3311.8554 7.09 32-3311.853739 8.15 34-3311.851963 9.26 36-3311.850093 10.43 Table S8. 6T-radical Cation S18
Interring SOMO (α) LUMO Eg(α) HOMO SOMO (β) Eg(β) 0-7.59938-5.29456 2.30-7.84266-6.64290 1.20 6-7.60700-5.28613 2.32-7.85272-6.65841 1.19 12-7.64075-5.28014 2.36-7.87830-6.68943 1.19 18-7.69109-5.26327 2.43-7.90524-6.74494 1.16 24-7.76265-5.23987 2.52-7.93953-6.81324 1.13 30-7.85272-5.21265 2.64-7.98171-6.89950 1.08 36-7.96157-5.19660 2.76-8.04429-7.00046 1.04 Table S9. 6T-radical Cation-TD Interring Eg(α) (ev) Eg(α) nm f Eg(β) (ev) Eg(β) nm f 0 1.787 693.9 1.8338 0.943 1314.3 0.4287 6 1.795 690.9 1.8101 0.947 1310.0 0.4377 12 1.814 683.5 1.7304 0.950 1305.8 0.4642 18 1.845 671.9 1.5789 0.945 1311.7 0.509 24 1.886 657.6 1.3247 0.934 1327.8 0.5584 30 1.906 650.4 0.6953 0.912 1359.1 0.5973 36 2.097 591.3 0.9214 0.886 1399.9 0.607 Table S10. 15T- Radical Cation Interring Relative Energy E (kcalmol -1 ) B3LYP/6-31G* 0-8278.2233486 15-8278.2185407 3.02 30-8278.2029144 12.82 45-8278.1742564 30.81 Table S11. 15T-Radical Cation Interring SOMO (α) LUMO Eg(α) HOMO SOMO (β) Eg(β) S19
0-6.21486-4.24202 1.97-6.01730-5.74546 0.27 15-6.30139-4.14950 2.15-6.07826-5.84097 0.24 30-6.52942-3.88473 2.64-6.25785-6.08179 0.18 45-6.84127-3.51193 3.33-6.52915-6.39881 0.13 Table S12. 6T-Dication Interring Relative Energy E (kcalmol -1 ) B3LYP/6-31G* 0-3311.5549219 6-3311.5541965 0.46 18-3311.5482967 4.16 24-3311.5431044 7.42 36-3311.5292081 16.14 Table S13. 6T-dication Interring HOMO (ev) LUMO (ev) HOMO- LUMO Gap (ev) 0-10.61661-9.32079 1.30 6-10.62286-9.32732 1.30 18-10.66477-9.37086 1.29 24-10.69797-9.40079 1.30 36-10.79130-9.45630 1.34 Table S14. 6T-Ionization Potential Interring Ionization Potential (ev) 6T E 0 5.733 2 5.735 0.001 4 5.739 0.005 6 5.744 0.010 8 5.751 0.016 10 5.760 0.025 S20
12 5.771 0.036 14 5.785 0.049 16 5.802 0.064 18 5.821 0.082 20 5.842 0.102 22 5.865 0.124 24 5.890 0.147 26 5.917 0.171 28 5.946 0.197 30 5.976 0.226 32 6.009 0.256 34 6.040 0.287 36 6.076 0.318 Table S15. Charge Distribution in 6T cation radical at different twist angle. Ring 6T-0 6T-90 6T-150 6T-180 Number 1 0.173 0.166 0.153 0.143 2 0.162 0.163 0.166 0.168 3 0.165 0.171 0.181 0.188 4 0.165 0.171 0.181 0.188 5 0.162 0.164 0.166 0.168 6 0.173 0.165 0.153 0.143 Table S16. Effect of twisting on band gap and relative energies in polythiophene (PBC- B3LYP/6-31G*). Twist Polythiophene angle Up-down twisting Spiral twisting Band gap (ev) E a (kcalmol -1 ) Band gap (ev) E (kcalmol -1 ) 0 2.06 2.06 15 2.15 0.08 2.26 0.06 30 2.47 0.59 2.81 0.41 60 3.47 3.40 4.30 2.27 90 5.09 7.30 4.91 3.45 Table S17. Effect of arrangement (head-to-tail (HT) and head-to-head(hh)) on band gap and relative energies in polythiophene (PBC-B3LYP/6-31G*). S21
Absolute energy Twist angle Band Gap (ev) E a (kcalmol -1 ) Poly(3-methylthiophene)-HT -1182.263432 0 2.00 Poly(3-methylthiophene)-HH -1182.261385 5 2.03 1.28 polycyclopenta[c]thiophene -1337.100232 0 2.03 Poly(3-ethylthiophene)-HT-conf1-1260.886823 0 1.94 0.40 Poly(3-ethylthiophene)-HT-conf2-1260.887454 20 2.18 0.00 Poly(3-ethylthiophene)-HH-conf1-1260.884015 22 2.18 2.16 Poly(3-ethylthiophene)-HH-conf2-1260.884869 32 2.43 1.62 Poly(3-ethylthiophene)-HH-planar b -1260.883879 0 1.97 2.24 a energy difference compared to minimal structure. b constrained to be planar S22