Organic Dyes Containing Fluorenylidene Functionalized Phenothiazine Donors As Sensitizers

Electronic Supplementary material

Organic Dyes Containing Fluorenylidene Functionalized Phenothiazine Donors as Sensitizers for Dye Sensitized Solar Cells

Ankita Saini,a K. R. Justin Thomas,*a Chun-Ting Lib and Kuo-Chuan Hob

a Organic Materials Laboratory, Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee, India. E-mail: ; Fax: +91 1332 286202; Tel: +91 1332 285376

b Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan.

Table of contents

TableS1 / Optical data of the dyes 5a-5b recorded in different solvents / S2
TableS2 / Calculated vertical transition energies and their oscillator strengths and configurations for the dyes / S2
Fig. 1 / 1H NMR of 2 recorded in CDCl3 / S3
Fig. 2 / 13C NMR of 2 recorded in CDCl3 / S3
Fig. 3 / 1H NMR of 3 recorded in CDCl3 / S4
Fig. 4 / 13C NMR of 3 recorded in CDCl3 / S4
Fig. 5 / 1H NMR of 4a recorded in CDCl3 / S5
Fig. 6 / 13C NMR of 4a recorded in CDCl3 / S5
Fig. 7 / 1H NMR of 4b recorded in CDCl3 / S6
Fig. 8 / 13C NMR of 4b recorded in CDCl3 / S6
Fig. 9 / 1H NMR of 5a recorded in CDCl3 / S7
Fig. 10 / 13C NMR of 5a recorded in CDCl3 / S7
Fig. 11 / 1H NMR of 5b recorded in CDCl3 / S8
Fig. 12 / 13C NMR of 5b recorded in CDCl3 / S8
TableS3 / Cartesian coordinates for the optimized geometry of 5a / S9
TableS4 / Cartesian coordinates for the optimized geometry of 5b / S11

S13

Table S1 Optical data of the dyes 5a-5b recorded in different solvents

Dyes / λmax, nm (ε max, M−1cm−1× 103)
THF / DCM+TEA / DCM+TFA / DMF
5a / 413 (52.5) / 397 (48.6) / 435 (45.9) / 389 (46.4)
5b / 437 (41.9), 341 (33.7) / 424 (36.9), 341 (24.2) / 463 (42.9), 347 (35.8) / 418 (38.2), 340 (23.4)

Table S2 Calculated vertical transition energies and their oscillator strengths and configurations for the dyes

Dye / λmaxcal, nm / f / Configuration / HOMO, eV / LUMO, eV / Band gap, eV
5a / 403.5 / 1.66 / HOMO-1 → LUMO (87%) / -6.23 / -1.95 / 4.28
380.7 / 0.55 / HOMO → LUMO+1 (82%)
313.8 / 0.25 / HOMO → LUMO+5 (26%), HOMO → LUMO+4 (23%), HOMO-3 → LUMO+1 (19%), HOMO-2 → LUMO+1 (10%), HOMO → LUMO+2 (5%)
291.0 / 0.20 / HOMO-5 → LUMO (49%), HOMO-1 → LUMO+2 (24%)
5b / 453.7 / 1.86 / HOMO-1 → LUMO (89%) / -6.23 / -2.07 / 4.16
381.3 / 0.80 / HOMO → LUMO+1 (87%)
321.2 / 0.19 / HOMO-1 → LUMO+2 (46%), HOMO-4 → LUMO (35%)
314.3 / 0.17 / HOMO → LUMO+6 (22%), HOMO → LUMO+4 (21%), HOMO-3 → LUMO+1 (15%)
301.3 / 0.10 / HOMO-3 → LUMO+1 (27%), HOMO-2 → LUMO+1 (20%), HOMO → LUMO+2 (16%)
295.3 / 0.15 / HOMO-1 → LUMO+2 (41%), HOMO-4 → LUMO (39%)

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Fig. 1 1H NMR of 2 recorded in CDCl3

Fig. 2 13C NMR of 2 recorded in CDCl3

Fig. 3 1H NMR of 3 recorded in CDCl3

Fig. 4 13C NMR of 3 recorded in CDCl3

Fig. 5 1H NMR of 4a recorded in CDCl3

Fig. 6 13C NMR of 4a recorded in CDCl3

Fig. 7 1H NMR of 4b recorded in CDCl3

Fig. 8 13C NMR of 4b recorded in CDCl3

Fig. 9 1H NMR of 5a recorded in CDCl3

Fig. 10 13C NMR of 5a recorded in CDCl3

Fig. 11 1H NMR of 5b recorded in CDCl3

Fig. 12 13C NMR of 5b recorded in CDCl3

Table S3 Cartesian coordinates for the optimized geometry of 5a

Energy = -3177.79847590 hartrees

Atom / X / Y / Z
C / -1.39406 / 4.308331 / -0.66002
C / -1.54076 / 5.604194 / -1.1549
C / -2.80698 / 6.149423 / -1.35048
C / -3.9294 / 5.388732 / -1.02453
C / -3.79016 / 4.107439 / -0.48948
C / -4.72516 / 1.578404 / -0.1747
C / -5.69659 / 0.61304 / -0.42338
C / -5.3739 / -0.75379 / -0.49636
C / -4.01672 / -1.09634 / -0.37919
C / -3.03629 / -0.13582 / -0.15934
C / -3.36605 / 1.225232 / -0.04601
C / -2.51449 / 3.534087 / -0.32095
C / -1.08705 / 1.786326 / 0.657504
C / -0.0983 / 1.34074 / -0.23494
C / 1.133561 / 0.935164 / 0.264567
C / 2.351936 / 0.416115 / -0.49914
C / 3.329916 / 0.167166 / 0.648804
C / 4.627334 / -0.3154 / 0.588929
C / 5.374083 / -0.47999 / 1.775951
C / 4.775658 / -0.14614 / 3.009596
C / 3.471618 / 0.333419 / 3.07364
C / 2.745971 / 0.492167 / 1.890411
C / 1.381831 / 0.971048 / 1.652692
C / 0.398861 / 1.413313 / 2.540672
C / -0.83562 / 1.820362 / 2.034407
C / 2.899958 / 1.465719 / -1.51119
C / 3.2832 / 2.835127 / -0.93813
C / 2.029601 / -0.89016 / -1.2847
C / 1.509936 / -2.07465 / -0.46119
N / -2.37917 / 2.212923 / 0.186669
S / -5.2412 / 3.260157 / 0.098797
H / -0.40035 / 3.901014 / -0.52538
H / -0.65246 / 6.17983 / -1.3968
H / -2.92534 / 7.152327 / -1.7476
H / -4.92751 / 5.793371 / -1.16285
H / -6.72341 / 0.930453 / -0.56736
H / -3.72221 / -2.13923 / -0.45764
H / -2.00332 / -0.44644 / -0.06848
H / -0.31314 / 1.321258 / -1.29967
H / 5.067753 / -0.58711 / -0.3666
H / 5.352936 / -0.23995 / 3.923361
H / 3.035835 / 0.589611 / 4.034888
H / 0.583825 / 1.443289 / 3.610437
H / -1.62034 / 2.169266 / 2.69743
H / 3.775073 / 1.026566 / -2.00824
H / 2.144885 / 1.600141 / -2.29747
H / 2.413903 / 3.2881 / -0.44388
H / 4.046337 / 2.709815 / -0.15975
H / 1.296002 / -0.63969 / -2.06268
H / 2.939339 / -1.19527 / -1.81869
H / 2.252891 / -2.35107 / 0.297349
H / 0.607275 / -1.77877 / 0.089021
C / 6.747943 / -0.98332 / 1.743727
C / 7.452482 / -1.6129 / 2.759799
S / 7.732645 / -0.82441 / 0.310456
C / 8.759614 / -1.96994 / 2.390174
H / 7.020911 / -1.83447 / 3.72808
C / 9.092862 / -1.62576 / 1.083603
H / 9.456834 / -2.48032 / 3.045878
C / 10.36355 / -1.89625 / 0.494216
C / 10.84117 / -1.64008 / -0.76285
H / 11.06229 / -2.38901 / 1.164609
C / 10.06305 / -1.00287 / -1.77578
C / 12.21836 / -2.01508 / -1.16592
N / 9.404742 / -0.48183 / -2.58274
O / 12.69134 / -1.81724 / -2.26492
O / 12.917 / -2.61521 / -0.1659
H / 13.79015 / -2.81298 / -0.54202
C / 3.812296 / 3.795095 / -2.01199
H / 4.682572 / 3.342342 / -2.50553
H / 3.051546 / 3.920605 / -2.79468
C / 4.200115 / 5.167114 / -1.45298
H / 4.572366 / 5.828388 / -2.24183
H / 3.342606 / 5.661012 / -0.98176
H / 4.986684 / 5.078665 / -0.69526
C / 1.193256 / -3.30113 / -1.32739
H / 2.093331 / -3.59417 / -1.88463
H / 0.444788 / -3.02866 / -2.0839
C / 0.685893 / -4.49565 / -0.51412
H / -0.23278 / -4.24532 / 0.028591
H / 0.468139 / -5.35385 / -1.15778
H / 1.428265 / -4.81495 / 0.225938
C / -6.36122 / -1.79781 / -0.78093
H / -5.98143 / -2.5824 / -1.43531
C / -7.65022 / -1.94544 / -0.38188
C / -8.46782 / -1.22858 / 0.629539
C / -8.5388 / -2.99959 / -0.93031
C / -8.15329 / -0.22491 / 1.54999
C / -9.76636 / -1.80326 / 0.649451
C / -8.30628 / -3.97167 / -1.9031
C / -9.81338 / -2.89463 / -0.32835
C / -9.13266 / 0.224763 / 2.439669
H / -7.15898 / 0.20189 / 1.592992
C / -10.741 / -1.34598 / 1.534233
C / -9.34097 / -4.84059 / -2.25851
H / -7.33769 / -4.06097 / -2.38722
C / -10.8465 / -3.7576 / -0.69096
C / -10.4204 / -0.32044 / 2.425601
H / -8.88653 / 1.007632 / 3.150951
H / -11.7333 / -1.78838 / 1.540809
C / -10.6015 / -4.73421 / -1.65898
H / -9.16603 / -5.60384 / -3.01109
H / -11.8274 / -3.67564 / -0.23114
H / -11.1705 / 0.046664 / 3.120049
H / -11.3955 / -5.41519 / -1.95118

Table S4 Cartesian coordinates for the optimized geometry of 5b

Energy = -3729.52821007 hartrees

Atom no. / X / Y / Z
C / -3.34599 / 4.428974 / -0.61982
C / -3.6528 / 5.70936 / -1.08014
C / -4.97782 / 6.119067 / -1.20545
C / -5.99656 / 5.237057 / -0.84624
C / -5.69661 / 3.969523 / -0.34562
C / -6.33387 / 1.34814 / -0.06811
C / -7.20273 / 0.290561 / -0.321
C / -6.73592 / -1.02975 / -0.45114
C / -5.34697 / -1.22619 / -0.37691
C / -4.46958 / -0.17166 / -0.15311
C / -4.94041 / 1.142408 / 0.006075
C / -4.36065 / 3.534715 / -0.2447
C / -2.70991 / 1.946458 / 0.642704
C / -1.72316 / 1.584064 / -0.28937
C / -0.43307 / 1.321918 / 0.155493
C / 0.794064 / 0.907551 / -0.65677
C / 1.849327 / 0.798154 / 0.443752
C / 3.184469 / 0.443873 / 0.328716
C / 4.00258 / 0.389496 / 1.477691
C / 3.435521 / 0.705208 / 2.730888
C / 2.093748 / 1.052043 / 2.85119
C / 1.296711 / 1.099656 / 1.704879
C / -0.12078 / 1.426026 / 1.527176
C / -1.10056 / 1.78873 / 2.453705
C / -2.39545 / 2.046776 / 2.003088
C / 1.174838 / 1.975734 / -1.72453
C / 1.450815 / 3.392217 / -1.20664
C / 0.576622 / -0.45058 / -1.38787
C / 0.200046 / -1.649 / -0.50882
N / -4.06031 / 2.228456 / 0.229301
S / -7.01837 / 2.954459 / 0.279978
H / -2.3098 / 4.126164 / -0.54075
H / -2.84341 / 6.380668 / -1.35075
H / -5.22074 / 7.110214 / -1.57451
H / -7.03744 / 5.534142 / -0.93201
H / -8.2619 / 0.498162 / -0.42496
H / -4.94454 / -2.22844 / -0.49528
H / -3.40719 / -0.37043 / -0.09714
H / -1.98492 / 1.514786 / -1.34151
H / 3.601773 / 0.182812 / -0.64017
H / 4.064799 / 0.698701 / 3.61461
H / 1.683098 / 1.292432 / 3.827546
H / -0.86748 / 1.86968 / 3.511334
H / -3.17919 / 2.329465 / 2.698093
H / 2.059772 / 1.611166 / -2.26338
H / 0.366309 / 2.012863 / -2.46711
H / 0.573482 / 3.765843 / -0.66302
H / 2.272518 / 3.367186 / -0.48014
H / -0.19977 / -0.30202 / -2.15064
H / 1.497031 / -0.68515 / -1.93947
H / 0.976676 / -1.81007 / 0.249275
H / -0.72365 / -1.4301 / 0.042354
C / 1.801476 / 4.37386 / -2.33294
H / 2.679308 / 4.001701 / -2.87864
H / 0.980263 / 4.398663 / -3.06212
C / 2.079562 / 5.792563 / -1.82746
H / 2.326962 / 6.46965 / -2.65124
H / 1.208009 / 6.205975 / -1.30734
H / 2.918802 / 5.804388 / -1.12305
C / 0.010604 / -2.93859 / -1.31873
H / 0.934174 / -3.15883 / -1.87131
H / -0.76594 / -2.78021 / -2.07965
C / -0.36307 / -4.14332 / -0.45013
H / -1.30033 / -3.96773 / 0.089931
H / -0.49182 / -5.04715 / -1.05406
H / 0.41262 / -4.34924 / 0.295864
C / -7.60998 / -2.16429 / -0.7582
H / -7.15838 / -2.88 / -1.44506
C / -8.87062 / -2.46341 / -0.35329
C / -9.74707 / -1.87685 / 0.691718
C / -9.64982 / -3.58312 / -0.93687
C / -9.52784 / -0.8839 / 1.65067
C / -10.9784 / -2.5845 / 0.69741
C / -9.32794 / -4.48554 / -1.95038
C / -10.9221 / -3.63544 / -0.32331
C / -10.5383 / -0.57538 / 2.565368
H / -8.58266 / -0.35792 / 1.704101
C / -11.9852 / -2.26725 / 1.60699
C / -10.2705 / -5.44234 / -2.33516
H / -8.36056 / -4.45363 / -2.44403
C / -11.8637 / -4.5861 / -0.71494
C / -11.7625 / -1.25074 / 2.537797
H / -10.3666 / 0.19915 / 3.306996
H / -12.9259 / -2.8107 / 1.602551
C / -11.529 / -5.49185 / -1.72405
H / -10.0252 / -6.15216 / -3.11968
H / -12.843 / -4.62569 / -0.246
H / -12.5386 / -0.99227 / 3.252321
H / -12.2513 / -6.23924 / -2.03916
C / 5.413115 / 0.008817 / 1.39148
C / 6.21692 / -0.54071 / 2.371619
S / 6.329953 / 0.224031 / -0.08699
C / 7.540042 / -0.79891 / 1.950262
H / 5.850938 / -0.78489 / 3.36154
C / 7.781878 / -0.45182 / 0.633611
H / 8.293467 / -1.2459 / 2.589351
C / 8.999662 / -0.58043 / -0.12521
C / 9.205544 / -0.32159 / -1.47571
S / 10.47545 / -1.12262 / 0.641495
C / 10.52452 / -0.55923 / -1.88736
H / 8.419173 / 0.020349 / -2.13822
C / 11.36662 / -1.00596 / -0.87239
H / 10.87626 / -0.41798 / -2.90355
C / 12.74388 / -1.31415 / -1.0666
C / 13.69494 / -1.7637 / -0.18884
H / 13.08735 / -1.1644 / -2.08637
C / 13.42278 / -2.01598 / 1.189073
C / 15.09042 / -2.02334 / -0.61614
N / 13.17028 / -2.21291 / 2.308819
O / 15.97186 / -2.42173 / 0.115625
O / 15.29591 / -1.7677 / -1.93596
H / 16.23168 / -1.97157 / -2.09627

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