Fused Bis-Benzothiadiazoles as Electron Acceptors Debin Xia, a,b Xiao-Ye Wang, b Xin Guo, c Martin Baumgarten,*,b Mengmeng Li, b and Klaus Müllen*,b a MIIT Key Laboratory of ritical Materials Technology for ew Energy onversion and torage, chool of hemistry and hemical Engineering, arbin Institute of Technology, 150001 arbin, P. R. hina. b Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany c Dalian Institute of hemical Physics, hinese Academy of ciences, 116023, Dalian, hina *E-mail: baumgart@mpip-mainz.mpg.de *E-mail: muellen@mpip-mainz.mpg.de Table of ontents Proposed reaction mechanism... 2 rystal structure of -BBT... 2 DFT calculations... 3 FET measurements... 4 1 MR and 13 MR spectra... 4 RM spectra... 9 rystal data... 10 alculation results... 13 1
Proposed reaction mechanism 2 2 Figure 1. Proposed reaction mechanism to produce compound 4. rystal structure of -BBT Figure 2. Planar offset for the dimer of -BBT 2
DFT calculations Figure 3. alculated absorption spectra of (a) Q-BBT and (b) -BBT according to TD-DFT calculations at the B3LYP/6-31G (d) level. Figure 4. Energy level diagram and frontier molecular orbitals according to DFT calculations at the B3LYP/6-31G (d) level.. 3
FET measurements Figure 5. utput characteristics of field-effect transistors fabricated using Q-BBT. 1 MR and 13 MR spectra 1 MR spectrum of ompound 5 in D 2 l 2 4
13 MR spectrum of ompound 5 in D 2 l 2 1 MR spectrum of ompound Q-BBT in D 2 4 5
13 MR spectrum of ompound Q-BBT in D 2 4 1 MR spectrum of ompound 4 in TF d8 6
1 MR spectrum of ompound 6 in D 2 l 2 13 MR spectrum of ompound 6 in D 2 l 2 7
1 MR spectrum of ompound -BBT in D 2 4 13 MR spectrum of ompound -BBT in D 2 4 8
RM spectra 9
rystal structure of 5 rystal data ambridge rystallographic Data entre deposition number: D 1410009 Table 1: rystallographic table. ompound 5 Molecular formula 66 4 4 4 2 Formula weight 925.05 gmol -1 Absorption coefficient µ = 0.079 mm -1 rystal size pace group 0.08 x 0.19 x 0.2 mm 3 ; light brown plate P 2 1 /n (monoclinic) Lattice parameters a = 9.9809(7) Å b = 15.5280(9) Å ß = 90.154(6) c = 15.1288(11) Å Volume 2344.7(3) Å 3 Z value 2 F (000) 968 alculated density d xray = 1.31 gcm -3 Temperature -80 can type ω-scans Theta range for data collection 2.4 < θ < 28.3 Limiting indices -13 h 11, -20 k 20, -20 l 20 Total number of reflections 14941 Unique number of reflections 5727 bserved number of reflections 3052 ( F /σ(f) > 4.0) tructure solution IR-2004 (Direct methods) R-values wr2 = 0.114 (R1 = 0.0471 for observed reflections, 0.1092 for all reflections) Goodness of fit = 0.918 Max hift / Error 0.001 * e.s.d Largest diff. peak and hole 0.22 and -0.19 eå -3 10
rystal structure of Q-BBT ambridge rystallographic Data entre deposition number: D 1400306 Table 1: rystallographic table. ompound Q-BBT Molecular formula 14 4 4 2 2 Formula weight 324.33 gmol -1 Absorption coefficient rystal size pace group µ = 4.079 mm -1 corrected with 6 crystal faces 0.02 x 0.02 x 0.2 mm 3 ; light brown needle 2/m (monoclinic) Lattice parameters a = 10.3036(19) Å b = 15.727(2) Å ß = 96.172(16) c = 3.8043(8) Å Volume 612.89(19) Å 3 Z value 2 F (000) 328 alculated density d xray = 1.757 gcm -3 Temperature -50 can type ω-scans Theta range for data collection 5.15 < θ < 66.35 Limiting indices -11 h 12, -18 k 18, -3 l 4 Total number of reflections 1820 Unique number of reflections 541 (R int = 0.0638) bserved number of reflections 354 ( F /σ(f) > 4.0) tructure solution IR-2004 (Direct methods) R-values wr2 = 0.2617 (R1 = 0.0801 for observed reflections, 0.1120 for all reflections) Goodness of fit = 1.076 Max hift / Error 0.001 * e.s.d Largest diff. peak and hole 0.52 and -0.47 eå -3 11
rystal structure of -BBT ambridge rystallographic Data entre deposition number: D 1400305 Table 1: rystallographic table. ompound -BBT Molecular formula 12 4 4 2 3 Formula weight 332.37 gmol -1 Absorption coefficient rystal size pace group µ = 0.62 mm -1 correction with 6 faces 0.04 x 0.06 x 0.7 mm 3 ; brown needle P-1 (triclinic) Lattice parameters a = 6.7778(7) Å α = 91.812(9) b = 9.6253(11) Å ß = 109.511(8) c = 9.8490(10) Å γ = 93.899(9) Volume 603.22(11) Å 3 Z value 2 F (000) 336 alculated density d xray = 1.83 gcm -3 Temperature -80 can type ω-scans Theta range for data collection 3.2 < θ < 28.3 Limiting indices -9 h 9, -12 k 12, -13 l 13 Total number of reflections 14727 Unique number of reflections 11764 bserved number of reflections 8156 ( F /σ(f) > 4.0) tructure solution IR-2004 (Direct methods) R-values wr2 = 0.1537 (R1 = 0.0573 for observed reflections, 0.0913 for all reflections) Goodness of fit = 1.027 Max hift / Error 0.001 * e.s.d Largest diff. peak and hole 0.45 and -0.43 eå -3 12
alculation results Table 2. Frontier molecular energy levels and absolute energies of Q-BBT and -BBT calculated by DFT method a M (ev) LUM (ev) M-LUM gap (ev) Engery (artree) Q-BBT -7.37-3.71 3.66-1701.9631968 -BBT -7.17-3.68 3.49-2023.861054 a alculated at the B3LYP/6-311G(d,p) level of theory Table 3. Frontier molecular energy levels and absolute energies of Q-BBT and -BBT calculated by DFT method a M (ev) LUM (ev) M-LUM gap (ev) Engery (artree) Q-BBT -7.16-3.50 3.66-1701.70650710 -BBT Q-BA -BA -6.95-6.23-6.05-3.45-2.46-2.06 3.50 3.77 3.99-2023.59866164-996.06827753-1317.95692935 a alculated at the B3LYP/6-31G(d) level of theory. Table 4. The selected absorption peaks of Q-BBT and -BBT calculated by TD-DFT method a Q-BBT -BBT Excited states Main transition configuration Transition energy (ev) Wavelength (nm) scillator strength (f) 1 M LUM 3.2105 386 0.1168 2 M-1 LUM 3.5775 346 0.0011 M LUM+1 3 M-2 LUM 3.6932 336 0.2669 M LUM+2 1 M-3 3.0234 410 0.0000 LUM+1 M-2 LUM 2 M-3 LUM 3.1118 398 0.0000 M-2 LUM+1 3 M LUM 3.2591 380 0.0100 a alculated at the B3LYP/6-31G(d) level of theory. 13
Table 5. oordinates (Å) of the optimized structure for Q-BBT in Figure 5 calculated at the B3LYP/6-311G(d,p) level of theory atom x y z -6.125956 0.825748 0.090628-6.240286-5.025798-3.688604-3.574275-4.788770-7.240455-8.517741-8.632488-7.467910-2.574099-1.296807-1.182060-2.346644-9.699285-10.841544-9.898706-0.115254 1.027000 0.084167-4.692066-5.122481-7.134501-7.533935-2.680053-2.280618-0.611964-1.482927-0.814407 0.623305 1.494271 1.628599 1.018252-0.425019-1.229020-1.617261-1.006917 0.436353 1.240358 1.647235 0.475990-0.860107-1.6359050-0.464658 0.871438 2.707952-2.696618 2.705263-2.308843-2.693926 2.320180 0.073773 0.027603-0.000461 0.016394 0.062299 0.133101 0.160653 0.143624 0.099676-0.042692-0.070044-0.053016-0.009268 0.203173 0.218480 0.173487-0.112231-0.127716-0.082556 0.076999 0.013666 0.144990 0.086609-0.054538 0.003836 Table 6. oordinates (Å) of the optimized structure for -BBT in Figure 5 calculated at the B3LYP/6-311G(d,p) level of theory. atom x y z -6.661299-6.201000-4.760321-4.126262-5.310166-7.944322-8.874854-8.437405-7.081860-4.023721-2.639183-2.025015-2.807383-10.175924-10.779238-9.423417-1.777957-0.320393-0.719221-5.516771-5.005375-8.261303-6.783296-4.455874-2.357816 1.050957-0.292836-0.365104 0.923829 2.234393 1.393221 0.320520-1.047685-1.340867-1.494147-1.338373-0.022941 1.135576 0.428327-1.094345-1.942170-2.325322-1.618313-0.045687 3.079240 2.846537 2.416381-2.369844-2.486360 2.120256-0.338155-0.123626 0.182060 0.199538-0.168291-0.633395-0.730220-0.519127-0.213008 0.437018 0.712739 0.724286 0.456920-1.007849-0.998881-0.643372 0.981052 1.224063 0.999868 1.006036-1.459763-0.789629-0.060229 0.435753 0.463143 14
Table 7. oordinates (Å) of the optimized structure for Q-BBT in Figure 3 calculated at the B3LYP/6-31G(d,) level of theory. atom x y z -1.10040000-1.22500000-0.12760000 1.10040000 1.22500000 0.12760000 2.21290000 3.43290000 3.55690000 2.45950000-2.21290000-3.43290000-3.55690000-2.45950000 0.24000000-0.24000000 4.52880000 5.83790000 4.75070000-4.52880000-5.83790000-4.75070000 2.17920000 2.62890000-2.17920000-2.62890000 0.77950000-0.56460000-1.37600000-0.77950000 0.56460000 1.37600000-1.54560000-0.99170000 0.34570000 1.11380000 1.54560000 0.99170000-0.34570000-1.11380000 2.58850000-2.58850000-1.62530000-0.53950000 0.76770000 1.62530000 0.53950000-0.76770000-2.64710000 2.20280000 2.64710000-2.20280000 0.03130000-0.00010000-0.03200000-0.03110000 0.00030000 0.03230000-0.06220000-0.06220000-0.03100000 0.00000000 0.06240000 0.06230000 0.03100000 0.00010000 0.06060000-0.06040000-0.08990000-0.07800000-0.03400000-0.03400000 0.07780000 0.03390000-0.08870000 0.02470000 0.08890000-0.02460000 Table 8. oordinates (Å) of the optimized structure for -BBT in Figure 3 calculated at the B3LYP/6-31G(d,) level of theory. atom x y z -0.17160000-0.18660000 1.03380000 1.96990000 1.41920000 1.37640000 2.66110000 3.59680000 3.25610000-1.29810000-2.44970000-2.46980000-1.34120000 3.10310000 4.78090000 4.77080000-3.57570000-4.78090000-3.61350000 1.46760000 1.88920000 0.63490000 4.02100000-1.28190000-1.38860000 1.38810000 0.05950000-0.42370000 0.54030000 2.21780000-1.69880000-1.98830000-1.01750000 0.25530000 2.05820000 1.37610000 0.04290000-0.62300000-3.14790000-3.09590000-1.41490000 1.88930000 0.68940000-0.48900000 3.03460000 2.65060000-2.51240000 1.04860000 3.14790000-1.71130000-0.17330000 0.02700000 0.30550000 0.31530000-0.03320000 0.55760000 0.81730000 0.82610000 0.57460000-0.46440000-0.55340000-0.35330000-0.06250000 1.06850000 1.34210000 1.08370000-0.82060000-0.83950000-0.46390000 1.17170000-1.34210000 0.55740000 0.58190000-0.62800000 0.09570000 15
Table 9. oordinates (Å) of the optimized structure for Q-BA in Figure 3 calculated at the B3LYP/6-31G(d,) level of theory. atom x y z -1.17560000-1.15540000 0.02070000 1.17560000 1.15540000-0.02070000 2.36780000 3.53390000 3.51380000 2.32820000-2.36780000-3.53390000-3.51370000-2.32820000-4.71410000-5.86800000-5.84790000-4.67410000 4.71410000 5.86800000 5.84790000 4.67410000-0.03890000 0.03900000 2.42820000 2.35560000-2.42820000-2.35560000-4.75910000-6.83050000-6.79390000-4.68610000 4.75920000 6.83050000 6.79390000 4.68610000 0.64440000-0.65680000-1.33550000-0.64440000 0.65670000 1.33550000-1.26460000-0.63070000 0.66790000 1.28940000 1.26450000 0.63060000-0.66800000-1.28940000 1.26560000 0.61620000-0.67840000-1.31540000-1.26570000-0.61640000 0.67830000 1.31530000 2.51180000-2.51180000-2.32840000 2.35370000 2.32830000-2.35370000 2.33080000 1.14420000-1.21650000-2.38090000-2.33090000-1.14430000 1.21630000 2.38080000-0.12990000 0.21900000 0.35820000 0.13020000-0.21870000-0.35790000 0.25300000 0.03990000-0.30820000-0.43160000-0.25280000-0.03980000 0.30840000 0.43190000-0.16720000 0.04950000 0.39660000 0.52480000 0.16720000-0.04970000-0.39670000-0.52480000-0.67320000 0.67360000 0.53660000-0.71860000-0.53640000 0.71880000-0.45170000-0.05710000 0.57580000 0.81150000 0.45170000 0.05680000-0.57600000-0.81150000 16
Table 10. oordinates (Å) of the optimized structure for -BA in Figure 3 calculated at the B3LYP/6-31G(d,) level of theory. atom x y z 0.92330000-0.61670000-0.53140000 0.73570000 1.60430000 1.25640000 1.01960000-1.80710000-2.93090000-2.85120000-1.65060000 1.19120000 2.51000000 3.37950000 2.91930000 2.97580000 4.28970000 5.15240000 4.69630000-4.13300000-5.25200000-5.17440000-3.97870000-1.84920000-1.59290000 0.48710000 3.61220000 2.28810000 4.66080000 6.23320000 5.42570000-4.22240000-6.23320000-6.09200000-3.94380000 2.79570000 1.95190000 0.66460000 0.22400000 1.17960000 3.76700000 3.05380000 2.56600000 1.89120000 0.59550000-0.01190000-1.00010000-1.26890000-0.30320000 0.92240000-2.49330000-2.76040000-1.79990000-0.57690000 2.49340000 1.81830000 0.53070000-0.07490000 3.62570000-1.06980000-1.79310000 1.72640000-3.30240000-3.76700000-2.01580000 0.19700000 3.55220000 2.31940000-0.02780000-1.13530000 0.10220000-0.29030000-0.65480000-0.66060000-0.30040000-0.93070000 1.53240000-0.22690000-0.53030000-0.89790000-0.95830000-0.97120000-0.92220000-0.55900000-0.24840000-1.23200000-1.18290000-0.82190000-0.51160000-0.47150000-0.77460000-1.13990000-1.20040000 0.07590000-1.25910000-1.26860000 0.05110000-1.53240000-1.43870000-0.78050000-0.21740000-0.17360000-0.72380000-1.38990000-1.50410000 17