Fused Bis-Benzothiadiazoles as Electron Acceptors

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1 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, arbin, P. R. hina. b Max Planck Institute for Polymer Research, Ackermannweg 10, Mainz, Germany c Dalian Institute of hemical Physics, hinese Academy of ciences, , Dalian, hina * baumgart@mpip-mainz.mpg.de * muellen@mpip-mainz.mpg.de Table of ontents Proposed reaction mechanism... 2 rystal structure of -BBT... 2 DFT calculations... 3 FET measurements MR and 13 MR spectra... 4 RM spectra... 9 rystal data alculation results

2 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

3 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

4 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

5 13 MR spectrum of ompound 5 in D 2 l 2 1 MR spectrum of ompound Q-BBT in D 2 4 5

6 13 MR spectrum of ompound Q-BBT in D MR spectrum of ompound 4 in TF d8 6

7 1 MR spectrum of ompound 6 in D 2 l 2 13 MR spectrum of ompound 6 in D 2 l 2 7

8 1 MR spectrum of ompound -BBT in D MR spectrum of ompound -BBT in D 2 4 8

9 RM spectra 9

10 rystal structure of 5 rystal data ambridge rystallographic Data entre deposition number: D Table 1: rystallographic table. ompound 5 Molecular formula Formula weight gmol -1 Absorption coefficient µ = 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 = (7) Å b = (9) Å ß = (6) c = (11) Å Volume (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 Unique number of reflections 5727 bserved number of reflections 3052 ( F /σ(f) > 4.0) tructure solution IR-2004 (Direct methods) R-values wr2 = (R1 = for observed reflections, for all reflections) Goodness of fit = Max hift / Error * e.s.d Largest diff. peak and hole 0.22 and eå -3 10

11 rystal structure of Q-BBT ambridge rystallographic Data entre deposition number: D Table 1: rystallographic table. ompound Q-BBT Molecular formula Formula weight gmol -1 Absorption coefficient rystal size pace group µ = 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 = (19) Å b = (2) Å ß = (16) c = (8) Å Volume (19) Å 3 Z value 2 F (000) 328 alculated density d xray = gcm -3 Temperature -50 can type ω-scans Theta range for data collection 5.15 < θ < Limiting indices -11 h 12, -18 k 18, -3 l 4 Total number of reflections 1820 Unique number of reflections 541 (R int = ) bserved number of reflections 354 ( F /σ(f) > 4.0) tructure solution IR-2004 (Direct methods) R-values wr2 = (R1 = for observed reflections, for all reflections) Goodness of fit = Max hift / Error * e.s.d Largest diff. peak and hole 0.52 and eå -3 11

12 rystal structure of -BBT ambridge rystallographic Data entre deposition number: D Table 1: rystallographic table. ompound -BBT Molecular formula Formula weight 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 = (7) Å α = (9) b = (11) Å ß = (8) c = (10) Å γ = (9) Volume (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 Unique number of reflections bserved number of reflections 8156 ( F /σ(f) > 4.0) tructure solution IR-2004 (Direct methods) R-values wr2 = (R1 = for observed reflections, for all reflections) Goodness of fit = Max hift / Error * e.s.d Largest diff. peak and hole 0.45 and eå -3 12

13 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 BBT 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 BBT Q-BA -BA 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 M-1 LUM M LUM+1 3 M-2 LUM M LUM+2 1 M LUM+1 M-2 LUM 2 M-3 LUM M-2 LUM+1 3 M LUM a alculated at the B3LYP/6-31G(d) level of theory. 13

14 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 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

15 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 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

16 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

17 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