Electronic supplementary materials
Stereomeric effects of bisPC71BM on polymer solar cell performance
Lin-Long Deng1, Xiang Li2, Shuai Wang2, Wen-Peng Wu2,3, Si-Min Dai2, Cheng-Bo Tian2, Yi Zhao2, Su-Yuan
Xie2*, Rong-Bin Huang2, Lan-Sun Zheng2
1
Pen-Tung Sah Institute of Micro-Nano Science and Technology, Xiamen University, Xiamen 361005, China.
2
State Key Lab for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for
Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering,
Xiamen University, Xiamen 361005, China
3
Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan
University, Kaifeng 475004, China
Table of contents:
1. Synthesis and purification of bisPC71BM isomers.
2. X-ray data for trans-bisPC71BM and cis-bisPC71BM.
3. Electron mobility of P3HT:trans-bisPC71BM and P3HT:cis-bisPC71BM films.
4. Computational details.
1
1. Synthesis and purification of bisPC71BM isomers.
The tosyl hydrazone of methyl benzoylbutyrate (673 mg, 1.8 mmol) and sodium methoxide (97 mg, 1.8 mmol) were suspended in dry
pyridine (15 mL) under an atmosphere of N2 and the mixture was stirred at room temperature for 25 min. To the resulting solution was
added a solution of C70 (840 mg, 1 mmol) in HPLC grade o-DCB (75 mL). The reaction mixture was heated to 70-75 oC in the dark for
13-15 hours until the formation of the [5,6]-adducts ceased (monitored by APCI-MS). The reaction mixture was allowed to cool to
ambient temperature. Subsequently, the reaction mixture was irradiated with a 400W sodium lamp for 30 hours until complete
isomerization of the [5,6] isomers to the corresponding [6,6] isomers was obtained (as monitored by HPLC). The volatile components
were evaporated in vacuo. The crude product was first purified by silica gel column chromatography using petroleum ether/toluene (1/1,
v/v) as eluents to remove unreacted C70 and PC71BM and then by HPLC using toluene as the eluent.
The separation and purification of bisPC71BM isomers requires three stages of HPLC runs, of which the last two runs were carried out
in a recyclic mode .All the separations were eluted with toluene at a flow rate of 4 mL/min at the room temperature. First step using a
5PBB column (I.D. 10 × 250 mm) and the samples ranging from 8.0 to 9.8 min were collected (Fig. S1a). Second step using a 5PBB
column (I.D. 10 × 250 mm) in a recyclic mode and after six cycles of HPLC runs, the peak containing the samples we wanted was
collected (Fig. S1b). The final step using a 5PYE column (I.D. 10 × 250 mm) in a recyclic mode and after eighteen cycles of HPLC runs,
the purified trans-PC70BM and cis-PC70BM was collected.
trans-bisPC71BM: 1H NMR (400MHz, CDCl3) δ: 7.954 (d, J = 7.2 Hz, 4H), 7.536 (t, J = 7.6 Hz, 4H), 7.439 (t, J = 7.6 Hz, 2H), 3.670 (s,
6H), 2.490 (m, 8H), 2.155 (m, 4H);
13C
NMR (100 MHz, CDCl3) δ: 173.41, 155.04, 154.41, 154.40, 153.33, 153.13, 151.63, 149.39,
149.25, 149.20, 149.13, 148.50, 147.96, 147.76, 144.82, 143.64, 142.59, 142.54, 142.13, 141.65, 141.32, 141.16, 141.09, 141.00, 139.35,
138.35, 137.55, 135.27, 131.61, 131.09, 131.01, 130.49, 128.49, 128.12, 70.71, 69.95, 51.64, 35.14, 34.23, 33.84, 21.75; FT-IR (KBr) ν
(cm-1): 2945 (m), 1737 (s), 1494 (w), 1443 (s), 1426 (s), 1251 (w), 1196 (w), 1160 (w), 795 (w), 754 (s), 700 (m), 665 (m), 575 (m), 539
(m); APCI-MS: M- = 1221.2 m/z (calcd. 1221.2).
cis-bisPC71BM: 1H NMR (400MHz, CDCl3) δ: 7.943 (d, J = 6.8 Hz, 4H), 7.523 (t, J = 7.2 Hz, 4H), 7.424 (t, J = 7.2 Hz, 2H), 3.684 (s,
6H), 2.505 (m, 8H), 2.156 (m, 4H); 13C NMR (100 MHz, CDCl3) δ: 173.43, 155.06, 154.37, 153.35, 153.10, 151.67, 151.58, 149.44,
149.37, 149.07, 148.41, 148.03, 147.82, 147.71, 144.58, 143.87, 143.63, 142.64, 142.47, 142.32, 142.16, 141.97, 141.77, 141.22, 141.02,
140.89, 139.31, 138.37, 137.72, 137.54, 137.36, 135.29, 135.23, 131.59, 131.23, 130.93, 130.77, 130.51, 130.45, 128.49, 128.10, 70.68,
69.96, 51.66, 35.14, 34.23, 33.85, 21.77; FT-IR (KBr) ν (cm-1): 2945 (m), 1737 (s), 1494 (w), 1443 (s), 1426 (s), 1250 (w), 1197 (w),
1158 (w), 795 (w), 754 (s), 700 (m), 665 (s), 575 (m), 533 (m); APCI-MS: M- = 1221.1 m/z (calcd. 1221.2).
2
Fig. S1 Multi-stage HPLC chromatograms for the separation of trans-PC71BM and cis-PC71BM. The regions of collected samples are
highlighted as black shadow.
3
Fig. S2 1H NMR spectrum of trans-bisPC71BM.
Fig. S3 13C NMR spectrum of trans-bisPC71BM.
4
Fig. S4 APCI-MS spectrum of trans-bisPC71BM.
Fig. S5 1H NMR spectrum of cis-bisPC71BM.
5
Fig. S6 13C NMR spectrum of cis-bisPC71BM.
Fig. S7 APCI-MS spectrum of cis-bisPC71BM.
2. X-ray data for trans-bisPC71BM and cis-bisPC71BM.
6
X-Ray Structure Determination of trans-bisPC71BM•C6H5CH3, and cis-bisPC71BM•C6H12. Single crystals of trans-bisPC71BM
suitable for X-ray analysis were obtained by solvent evaporation from a toluene solution. Single crystals of cis-bisPC71BM suitable for
X-ray analysis were obtained by solvent evaporation from a cyclohexane solution. Diffraction data were collected on a Super Nova
diffractometer system equipped with a Super Nova (Cu) X-ray source (λ = 1.54184 Å) radiation in the ω scan mode at 173K. Structure
solution and refinement were performed using Bruker SHELXTL-97 program. CCDC 920165 and 920166 contain the supplementary
crystallographic data of trans-bisPC71BM and cis-bisPC71BM. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. The refined CIFs were checked at the web site
‘http://checkcif.iucr.org/’. All the alert questions in the ‘Check CIF Reports’ have been carefully checked to make sure the validity of the
reported crystallographic data. Crystal data and experimental parameters are summarized in Table S1.
Table S1 Crystal data and experimental parameters for trans-bisPC71BM•C6H5CH3, and cis-bisPC71BM•C6H12.
trans-bisPC71BM•C6H5CH3
cis-bisPC71BM•C6H12
formula
C101 H36 O4
C100 H40 O4
crystal system
triclinic
triclinic
space group
P-1
P-1
a, Å
9.9613(6)
10.0411(4)
b, Å
14.8330(11)
16.0700(8)
c, Å
21.1924(15)
17.8536(8)
α, deg
107.137(6)
96.956(4)
β, deg
95.342(5)
94.014(3)
γ, deg
105.771(6)
92.562(4)
V, Å 3
2828.1(3)
2848.5(2)
Z
2
2
T, K
173(2)
173(2)
crystal description
dark-red
dark-red
crystal size, mm
0.20×0.10×0.10
0.20×0.15×0.05
2θmin, 2θmax, deg
3.28, 74.41
3.50, 74.19
no. refl. measured (I>2σ(I))
9293
8129
no. parameters
949
1055
7
R1, wR2 (all data)
0.0851,0.2220
0.0835, 0.2364
R1, wR2 (I>2σ(I))
0.0701, 0.1967
0.1050 ,0.2608
GOF on F2
1.052
1.042
Crystal structure of trans-bisPC71BM•C6H5CH3.
The structure of trans-bisPC71BM•C6H5CH3 is presented in Fig. S8a. The bodies of fullerenes forming a one-dimensional stacking motif
that extends along the a-axis and the corresponding closet approach of carbon atoms range between 3.24 and 3.40 Å (Fig. S8c). The
adjacent stacks aligned in an antiparallel fashion, which are defined by two short intermolecular C···C contacts of 3.33 Å and a CH-π
interaction between two adjacent phenyl groups of two trans-bisPC71BM molecules (Fig. S8b). The intermolecular interactions between
two adjacent C70 molecules are shown in Fig. S8d.
Fig. S8 Crystal structure of trans-bisPC71BM•C6H5CH3. (a) Ellipsoids are drawn at the 50% level. Key: gray, carbon; white, hydrogen;
red, oxygen.
(b) Crystal stacking structure viewed along the a-axis. (c) Crystal stacking structure viewed along the b-axis. (d) Short
intermolecular C···C contacts (less than 3.40 Å) between two adjacent C70 molecules .Inside and outside the crystal cell are indicated by
dashed lines. The C···C distances around a representative molecule are given in angstroms.
Crystal structure of cis-bisPC71BM•C6H12.
8
The structure of cis-bisPC71BM•C6H12 is presented in Fig. S9a. The fullerene bodies are densely packing, forming a two-dimensional
network of close contacts. Fig. S9c shows a zigzag chain, aligned parallel to the b-axis, view along the a-axis. There are five short
intermolecular C···C contacts, ranging between 3.05 and 3.27 Å. The fullerenes are organized into one-dimensional chain along the
a-axis (Fig. S9b). The short intermolecular C···C contacts range between 3.20 and 3.35 Å. The intermolecular interactions between two
adjacent C70 molecules are showed in Fig. S9d.
Fig. S9 Crystal structure of cis-bisPC71BM•C6H12. (a) Ellipsoids are drawn at the 50% level. Key: gray, carbon; white, hydrogen; red,
oxygen.
(b) Crystal stacking structure viewed along the b-axis. (c) Crystal stacking structure viewed along the a-axis. (d) Short
intermolecular C···C contacts (less than 3.36 Å) between two adjacent C70 molecules. Inside and outside the crystal cell are indicated by
dashed lines. The C···C distances around a representative molecule are given in angstroms.
3. Electron mobility of P3HT:trans-bisPC71BM and P3HT:cis-bisPC71BM films.
9
Fig. S10 Measured space-charge limited J-V characteristics of the P3HT: fullerene blend devices under dark conditions for electron-only
devices.
4. Computational details.
Full geometry optimizations and DFT calculations of bisPC71BM isomers have been carried out at B3LYP/6-31G(d) level in Gaussian 09
package. The energy levels of HOMO and LUMO of bisPC71BM isomers were calculated at B3LYP/6-31+G(d, p) level, and the surface
plots of HOMO and LUMO orbitals were generated with Gaussianview.
Fig. S11 The optimized geometries of trans-bisPC71BM (left) and cis-bisPC71BM (right): gray ball is carbon atom, red ball is oxygen
atom and white ball is hydrogen atom.
10
Fig. S12 HOMO (left) and LUMO (right) surface plots for trans-bisPC71BM computed using B3LYP/6-31G(d).
Fig. S13 HOMO (left) and LUMO (right) surface plots for cis-bisPC71BM computed using B3LYP/6-31G(d).
Table S2 HOMO and LUMO energy levels of bisPC71BM isomers calculated by B3LYP/6-31+G (d, p) level.
Compound
HOMO/eV
LUMO/eV
trans-bisPC71BM
-5.74
-3.31
cis-bisPC71BM
-5.75
-3.32
Table S3 Cartesian coordinates and total energy of trans-bisPC71BM obtained at B3LYP/6-31G(d) level.
O
7.736004
11.635260
-0.931910
C
1.510567
7.162259
6.989376
C
4.955437
3.869201
1.897947
C
1.352348
2.324302
7.664693
C
3.197328
8.112996
2.929924
C
-0.008950
6.966254
5.245618
C
4.662857
6.360991
1.943543
C
0.938052
1.630317
2.599715
C
5.029196
6.976246
6.428913
C
5.774678
6.794695
5.280143
C
2.842658
2.652662
1.439823
C
1.056703
7.787987
5.779361
C
3.611701
1.401334
7.313498
C
3.394430
3.578014
8.189733
C
6.248692
5.476022
4.959698
11
C
0.301780
5.273887
2.150431
C
2.386090
6.353980
1.415738
C
2.133935
3.867782
1.230690
C
5.523451
7.534854
4.013804
C
4.870733
2.125439
7.105836
C
1.732038
0.553440
6.010865
C
3.821979
7.807516
6.418941
C
3.911846
0.089402
5.162784
C
4.504741
1.508372
2.621020
C
-0.533998
3.080056
3.685892
C
1.615535
0.359266
4.583519
C
1.268115
4.821133
7.846464
C
4.314420
5.049873
1.433205
C
1.871418
8.186770
3.490432
C
3.472453
5.971794
7.854578
C
2.920445
5.046228
1.104317
C
5.380402
4.581339
7.091394
C
5.618502
1.934353
5.958957
C
5.303951
0.896697
4.939666
C
6.134814
5.282655
3.544787
C
0.771308
3.988198
1.772720
C
4.717654
3.457381
7.655430
C
4.236525
2.649607
1.768932
C
0.619203
1.037722
3.868046
C
-0.166925
2.132119
5.920498
C
-0.227376
5.851106
6.146321
C
2.868076
7.161025
7.294600
C
-0.455693
5.467852
3.352487
C
6.056650
2.888641
3.879108
C
1.095945
6.466984
1.923580
C
6.128524
4.384452
5.860990
12
C
0.637761
3.582882
7.553343
C
0.848794
1.421250
6.667770
C
0.715884
5.969691
7.220131
C
0.827533
7.403818
2.978652
C
6.172431
3.082864
5.293753
C
-0.761544
4.379664
4.213684
C
5.895340
3.992868
2.999341
C
2.702136
4.820297
8.175145
C
3.452623
7.190077
1.923498
C
5.571633
9.036990
3.805337
C
1.988606
8.382510
4.917150
C
5.434416
11.067297
5.288116
H
4.486406
11.304200
4.812017
C
3.129031
0.507388
6.365254
C
2.709382
2.322606
7.971105
C
2.937824
0.193287
4.035765
C
-0.305788
3.462748
6.480077
C
0.223154
2.887809
2.483147
C
-0.121037
6.778136
3.875406
C
7.338266
9.610919
5.543723
H
7.879074
8.708785
5.272609
C
7.572237
11.361448
0.381847
O
7.319274
12.207667
1.212941
C
3.244665
0.785728
2.818443
C
-0.279513
1.944325
4.550483
C
-0.642662
4.579036
5.667630
C
5.934865
9.548740
2.403520
H
5.376733
8.985966
1.648695
H
5.607739
10.591549
2.332919
C
5.955075
11.922536
6.258191
H
5.409900
12.821636
6.532282
13
C
6.118618
9.900851
4.920554
C
7.769221
9.880344
0.650651
H
8.817836
9.649442
0.419637
H
7.176554
9.316137
-0.080552
C
7.861436
10.466047
6.515390
H
8.808380
10.224496
6.990698
C
7.435066
9.463891
2.087151
H
7.777855
8.431500
2.231657
H
7.997955
10.093050
2.783841
C
7.170922
11.623358
6.875888
H
7.576444
12.287782
7.634066
C
5.590295
6.480604
2.962957
C
2.228863
1.516896
2.092584
C
4.795602
5.856950
7.318599
C
7.597830
13.018781
-1.296088
H
7.759542
13.055018
-2.373805
H
8.339750
13.629961
-0.775186
H
6.598580
13.384416
-1.044946
C
5.428609
1.616598
3.642624
C
5.252821
-0.607866
5.146265
C
4.185820
8.456226
3.994376
C
3.388360
8.432932
5.257639
O
5.561717
-4.622473
9.927890
O
4.175540
-4.842064
8.156293
C
5.795087
-1.149352
6.477966
H
5.684647
-0.392523
7.260635
H
6.874564
-1.308607
6.352610
C
5.043090
-4.230754
8.741306
C
5.694525
-2.945693
8.266593
H
6.776088
-3.123493
8.194283
H
5.573399
-2.193853
9.057860
14
C
5.124071
-2.451017
6.936003
H
4.044413
-2.293597
7.044371
H
5.245187
-3.232369
6.178937
C
5.010648
-5.833602
10.470400
H
5.173909
-6.671227
9.786914
H
3.936891
-5.723558
10.644687
H
5.536465
-5.998656
11.411349
C
5.084030
-3.323358
2.461460
H
4.386131
-4.081104
2.115929
C
6.858974
-1.374009
3.360790
H
7.551776
-0.610616
3.706045
C
4.714907
-2.468303
3.501516
H
3.733071
-2.564819
3.955560
C
5.597733
-1.483802
3.962116
C
7.229129
-2.226675
2.321372
H
8.209363
-2.124653
1.863404
C
6.341172
-3.204587
1.868305
H
6.627032
-3.867930
1.056522
Total energy -3899.6248532 a.u.
Table S4 Cartesian coordinates and total energy of cis-bisPC71BM obtained at B3LYP/6-31G(d) level.
C
-0.173336
2.183847
12.220667
C
-2.848071
3.887517
7.093128
C
-0.265655
2.158043
9.804260
C
-0.017897
2.889044
10.997061
C
-2.265628
2.524674
15.318350
C
-1.465710
0.756815
13.532603
C
-4.034087
0.641462
7.936479
C
-2.707704
0.151935
13.581086
C
-1.994729
4.709888
7.815504
15
C
-3.390797
-0.408423
9.949067
C
-0.860696
4.157956
8.562545
C
-2.541833
3.973464
15.084235
C
-0.906992
0.877347
9.842885
C
-1.653294
0.703588
8.625738
C
-2.315597
6.354472
11.047669
C
-6.357937
5.274755
11.214021
C
-5.813243
5.724528
9.981013
C
-0.603348
2.800516
8.562681
C
-7.016796
3.959067
11.253715
C
-0.672538
4.211010
13.460992
C
-1.076878
1.899924
14.402015
C
-6.741972
1.808028
12.472943
C
-4.795594
5.156690
7.937572
C
-7.079274
3.195226
10.057080
C
-2.347077
5.839631
13.499559
C
-4.615122
2.886435
15.130598
C
-0.415835
2.853513
13.470061
C
-3.718810
6.068075
13.549662
C
-3.596984
1.865589
15.153663
C
-4.712238
-0.162344
12.419878
C
-1.650071
5.946580
12.236490
C
-1.747559
4.778945
14.279965
C
-6.592479
3.719838
8.796070
C
-4.270779
4.092684
7.191289
C
-5.971514
4.960412
8.758845
C
-0.246265
4.324237
10.990367
C
-4.534040
6.371304
9.925957
C
-4.442037
6.396773
12.335100
C
-1.742954
5.920295
9.820438
C
-5.784723
5.012648
13.638825
16
C
-3.767091
6.590423
11.100759
C
-3.297985
-0.382759
12.370800
C
-2.895217
0.098626
8.685480
C
-5.819055
2.691119
14.439761
C
-1.333587
1.827600
7.704583
C
-4.549425
5.225668
14.363321
C
-0.001425
2.841817
16.558783
C
-5.720925
5.750158
12.391862
C
-6.203353
1.431190
8.804137
C
-2.534084
5.787458
8.616582
C
-0.720872
4.917436
9.788785
C
-3.786302
0.711205
14.403233
C
0.582537
4.606991
18.122796
H
0.270600
5.366592
18.834518
C
-6.405820
3.772286
13.676266
C
-6.522427
1.093201
11.265640
C
-6.833548
1.782312
10.063643
C
-6.065221
2.622041
8.013296
C
-3.905742
6.016157
8.666687
C
-5.013856
0.519161
13.660032
C
-6.016319
1.483775
13.687522
C
-5.465892
0.069893
11.236133
C
-3.968153
4.177654
15.090286
C
1.936934
4.418204
17.847268
H
2.685766
5.030681
18.342120
C
-1.017136
1.920142
15.919564
C
-6.987753
3.221087
12.467850
C
1.362308
2.658705
16.291175
H
1.669452
1.901202
15.574530
C
-0.379941
3.823437
17.482870
H
-1.432582
3.981827
17.698854
17
C
2.324865
3.440230
16.928900
H
3.377353
3.287467
16.705617
C
-2.602452
-0.374972
11.131249
C
-1.316563
0.300252
11.074586
C
-2.589300
2.434136
6.870465
C
-3.903514
1.779709
7.149851
C
-0.428988
2.724254
5.451710
C
-0.814696
0.903329
12.258668
C
-4.917954
2.801362
7.228492
C
-0.879677
3.665892
4.518394
H
-1.945916
3.800924
4.362055
C
-1.580948
0.454550
5.501348
H
-2.124786
-0.224231
6.165540
H
-0.584122
0.015767
5.359659
C
-1.390922
1.816664
6.186584
C
0.951127
2.567451
5.639063
H
1.313429
1.842822
6.363998
C
0.029483
4.435486
3.789997
H
-0.337665
5.162365
3.070637
C
1.401246
4.273159
3.985651
H
2.108548
4.874651
3.421149
C
-2.311381
0.539460
4.155101
H
-3.303140
0.984534
4.298162
H
-1.774280
1.202165
3.469080
C
1.860539
3.335469
4.912994
H
2.927154
3.203911
5.074231
O
-3.604680
0.229000
1.637388
C
-3.189295
-0.776143
2.171921
C
-2.468751
-0.836878
3.505431
H
-1.492702
-1.312351
3.338546
H
-3.022766
-1.525888
4.156970
18
O
-3.315041
-2.012541
1.637261
C
-3.987010
-2.068780
0.368349
H
-3.445802
-1.483797
-0.380245
H
-5.004707
-1.678502
0.454016
H
-4.003011
-3.123543
0.092084
C
-0.627227
4.944197
12.211683
C
-4.804768
-0.187945
10.003471
C
-5.200819
0.466782
8.775632
C
-0.453365
-1.190433
19.117155
C
-1.837427
-0.675651
18.779553
H
-2.412445
-0.555981
19.702791
O
0.221873
-1.909902
18.411041
C
1.309212
-1.075065
20.680271
H
2.030552
-0.718674
19.939989
H
1.394455
-2.161791
20.763315
H
1.485193
-0.601246
21.646443
C
-1.143784
0.570171
16.641518
H
-0.140449
0.135247
16.714410
H
-1.733673
-0.126170
16.038252
C
-1.776409
0.678449
18.036233
H
-1.225419
1.398036
18.652322
H
-2.800445
1.060687
17.941139
O
-0.026179
-0.700560
20.304088
H
-2.328732
-1.428373
18.154996
Total energy -3899.6237632 a.u.
19