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TRANSCRIPT
Synthesis and characterization of dithienopyrrole-based organic dyes
containing electron-withdrawing linkers
Sunil Kumar, 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.
b Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan.
*Corresponding author:
E-mail address: [email protected], Fax: +91 1332 273560, Tel.: +91 1332 285376.
Supplementary Information
Scheme S1 Synthesis of reaction intermediates. S1
Fig. S1 Absorption spectra of the dye DTP-TS recorded in DCM before and after the addition of TEA/TFA.
S6
Fig. S2 Absorption spectra of the dye DTP-QP recorded in DCM before and after the addition of TEA/TFA.
S7
Fig. S3 Absorption spectra of the dye DTP-QS recorded in DCM before and after the addition of TEA/TFA.
S7
Fig. S4 Normalized absorption spectra of the dye DTP-TP dye recorded in different solvents. S8Fig. S5 Normalized absorption spectra of the dye DTP-QP dye recorded in different solvents. S8Fig. S6 Normalized absorption spectra of the dye DTP-QS dye recorded in different solvents. S9Fig. S7 Absorption spectra of the aldehyde precursors recorded in DCM. S9
Fig. S8 Normalized emission spectra of the dyes recorded in DCM. S10Fig. S9 Differential pulse voltammograms of the dyes recorded in DCM. S10
Table S1 Comparison between experimental and calculated maximum absorption wavelength in THF solvent.
S11
Fig. S10 Computed interplanar angles between the different aryl groups in the dyes. S11
Fig. S11 1H NMR spectra of S1 recorded in CDCl3. S12
Fig. S12 13C NMR spectra of S1 recorded in CDCl3. S13
Fig. S13 1H NMR spectra of S2 recorded in CDCl3. S14
Fig. S14 13C NMR spectra of S2 recorded in CDCl3. S15
Fig. S15 1H NMR spectra of S3 recorded in CDCl3. S16
Fig. S16 13C NMR spectra of S3 recorded in CDCl3. S17
Fig. S17 1H NMR spectra of S4 recorded in CDCl3. S18
Fig. S18. 13C NMR spectra of S4 recorded in CDCl3. S19
Fig. S19 1H NMR spectra of 7 recorded in CDCl3. S20
Fig. S20 13C NMR spectra of 7 recorded in CDCl3. S21
Fig. S21 1H NMR spectra of 8 recorded in CDCl3. S22
Fig. S22 13C NMR spectra of 8 recorded in CDCl3. S23
S1
Fig. S23 1H NMR spectra of 9 recorded in CDCl3. S24
Fig. S24 13C NMR spectra of 9 recorded in CDCl3. S25Fig. S25 1H NMR spectra of 10 recorded in CDCl3. S26Fig. S26 13C NMR spectra of 10 recorded in CDCl3. S27
Fig. S27 1H NMR spectra of DTP-TP recorded in DMSO-d6. S28
Fig. S28 13C NMR spectra of DTP-TP recorded in DMSO-d6. S29
Fig. S29 1H NMR spectra of DTP-TS recorded in DMSO-d6. S30
Fig. S30 13C NMR spectra of DTP-TS recorded in DMSO-d6. S31
Fig. S31 1H NMR spectra of DTP-QP recorded in DMSO-d6. S32
Fig. S32 13C NMR spectra of DTP-QP recorded in DMSO-d6. S33
Fig. S33 1H NMR spectra of DTP-QS recorded in CDCl3. S34
Fig. S34 13C NMR spectra of DTP-QS recorded in CDCl3 with small amount of TFA. S35
S2
Scheme S1 Synthesis of reaction intermediates
Synthesis of S1. It was obtained from 4,7-dibromo-2-butyl-2H-benzo[d][1,2,3]triazole (1.00 g, 3mmol) and (4-
formylphenyl)boronic acid (0.400 g, 1 mmol) was kept at 85 °C for 3 h nitrogen atmosphere. On the completion of
reaction (monitored through TLC), the mixture was poured into water and extracted with chloroform. The organic
layer was washed with brine solution followed by water and dried over anhydrous Na2SO4. The volatiles were
removed to obtain a solid residue. The obtained crude product was further purified by column chromatography using
silica as stationary phase and hexane:chloroform (1:1) as eluent. Colorless solid; yield 0.390 g (37%); m.p. 58-60
°C; IR (KBr, cm-1) 1694 (C=O); 1H NMR (399.78 MHz, CDCl3) δ; 0.99 (t, J = 7.6 Hz, 3 H), 1.41-1.46 (m, 2 H),
2.13-2.17 (m, 2 H), 4.79-4.83 (m, 2 H), 7.51 (d, J = 7.2 Hz, 1 H), 7.68 (d, J = 7.6 Hz, 1 H), 8.02 (dd, J = 2.0, 8.4 Hz,
2 H), 8.18 (d, J = 8.4 Hz, 2 H) 9.95 (s, I H); 13C NMR (100.53 MHz, CDCl3) δ 192.0, 191.9, 142.7, 132.8, 130.23,
129.6, 129.3, 129.1, 125.8, 111.1, 57.1, 32.3, 32.2, 19.9, 13.6. HRMS calcd for C17H16BrN3O [M+Na]+ m/z 380.0369
found 380.0367.
Synthesis of S2. A mixture of 4,7-dibromo-2-butyl-2 H-benzo[d][1,2,3]triazole (1.00 g, 3 mmol), (5-(1,3-
dioxolan-2-yl)thiophen-2-yl)tributylstannane (1.66 g, 3 mmol) , Pd(PPh3)2Cl2 (21 mg, 0.03 mmol) and 10 mL DMF
was heated at 80 °C for 24 h under nitrogen atmosphere. On the completion of reaction (monitored through TLC),
S3
the mixture was poured into water and extracted with chloroform. The organic layer was washed with brine solution
followed by water and dried over anhydrous Na2SO4. The volatiles were removed to obtain a crude product.
Further, crude product was dissolved in glacial acetic acid (5 mL) and heated to 60 °C. After 30 min, it was
treated with 10 mL water and the heating was continued for further 6 h. After cooling to room temperature, the
reaction mixture was extracted with chloroform. The organic layer was washed with brine solution followed by
water and dried over anhydrous Na2SO4. The volatiles were removed and the crude product obtained further purified
by column chromatography using alumina as stationary phase and hexane:chloroform (1:4) as eluent. Yellow oil;
yield 0.370 g (59%); IR (KBr, cm-1) 1667 (C=O); 1H NMR (399.78 MHz, CDCl3) δ 0.98-1.01 (m, 3 H), 1.39-1.46 (m,
2 H), 2.12-2.19 (m, 2 H), 4.79-4.83 (m, 2 H), 7.60 (s, 2 H), 7.80 (d, J = 3.6 Hz, 1 H), 8.11 (d, J = 3.6 Hz, 1 H), 9.95
(s, 1 H); 13C NMR (100.53 MHz, CDCl3) δ 183.1, 148.6, 144.3, 143.1, 141.5, 137.2, 136.9, 129.2, 128.5, 128.1,
127.9, 124.5, 123.0, 111.7, 57.2, 57.0, 32.2, 19.9, 13.6. HRMS calcd for C15H14BrN3OS [M+Na]+ m/z 385.9933
found 385.9922.
Synthesis of S3. A mixture of 5,8-dibromo-2,3-bis(4-(tert-butyl)phenyl)quinoxaline (1.1 g, 2 mmol) (4-
formylphenyl)boronic acid (0.150 g, 1 mmol), K2CO3 (0.551 g, 3 mmol), PPh3 (1 mg, 0.01 mmol), Pd(PPh3)Cl2 (7
mg, 0.01 mmol) and 25 mL DMF:H2O (4:1) was kept at 85 °C for 3 h nitrogen atmosphere. On the completion of
reaction (monitored through TLC), the mixture was poured into water and extracted with chloroform. The organic
layer was washed with brine solution followed by water and dried over anhydrous Na2SO4. The volatiles were
removed to obtain a solid residue. The obtained crude product was further purified by column chromatography using
silica as stationary phase and hexane:chloroform (1:1) as eluent. colorless solid; yield 0.171g (30%); m.p. 218-220
°C; IR (KBr, cm-1) 1697 (C=O); 1H NMR (399.78 MHz, CDCl3) δ; 1.30 (s, 9 H), 1.34 (s, 9 H), 7.31 (d, J =4.4 Hz, 2
H), 7.39 (d, J = 8.4 Hz, 2 H), 7.51 (d, J = 8.4 Hz, 2 H), 7.66-7.69 (m, 3 H), 7.97 (d, J = 8.0 Hz, 2 H), 8.03 (d, J = 8.0
Hz, 2 H), 8.11 (d, J = 7.6 Hz, 1 H) 10.1 (s, 1 H); 13C NMR (100.53 MHz, CDCl3) δ 192.4, 153.3, 153.0, 152.8,
152.8, 144.1, 138.6, 135.6, 135.5, 132.7, 131.6, 130.1, 129.9, 129.8, 129.5, 125.4, 125.3, 125.19, 125.15, 125.1,
124.5, 31.5, 31.4, 31.3. HRMS calcd for C35H33BrN2O [M+H]+ m/z 577.1848 found 577.1822.
Synthesis of S4. A mixture of 4,7-dibromo-2-butyl-2H-benzo[d][1,2,3]triazole (1.104 g, 2 mmol),
tributyl(thiophen-2-yl)stannane(0.940 g, 2 mmol), Pd(PPh3)Cl2 (0.014 g, 0.02 mmol) and 10 mL DMF was heated at
80 °C for 24 h under a nitrogen atmosphere. On completion of the reaction, the mixture was poured into water and
S4
extracted with chloroform. The organic layer was washed with brine solution followed by water and dried over
anhydrous Na2SO4. The volatiles were removed by rotary evaporator to obtain a crude product.
To the above product in 5 mL DMF taken at 0 °C, (0.100 g, 648 mmol) POCl 3 was added. Reaction mixture
was continued at same conditions for 30 min and at 45 °C for next 4 h. On the completion of reaction (monitored
through TLC), it was quenched by addition of ice-water and neutralized with sodium hydroxide solution. The
organic layer was washed with brine solution followed by water and dried over anhydrous Na 2SO4. The volatiles
were removed by rotary evaporator to obtain a crude product. The crude product obtained after the evaporation
further purified by column chromatography using silica as stationary phase and hexane:chloroform (2:3) as eluent.
Orange solid; yield 0.160 g (60%); IR (KBr, cm -1) 1666 (C=O); 1H NMR (399.78 MHz, CDCl3) δ; 1.32-1.36 (m, 18
H), 7.38-7.43 (m, 4 H), 7.66 (dd, J = 5.2, 4.4 Hz, 4 H), 7.82 (d, J = 4.0 Hz, 1 H), 7.88 (d, J = 4.0 Hz, 1 H), 7.98 (d, J
= 8.4 Hz, 1 H), 8.06 (d, J = 8.0 Hz, 1 H), 9.99 (s, 1 H) 13C NMR (100.53 MHz, CDCl3) δ 183.5, 135.8, 132.7, 130.2,
130.0, 128.2, 127.5 125.5, 125.4, 31.3. HRMS calcd for C33H31BrN2OS [M+H]+ m/z 583.1413 found 583.1423.
Fig. S1 Absorption spectra of the dye DTP-TS recorded in DCM before and after the addition of TEA/TFA
S5
Fig. S2 Absorption spectra of the dye DTP-QP recorded in DCM before and after the addition of TEA/TFA
Fig. S3 Absorption spectra of the dye DTP-QS recorded in DCM before and after the addition of TEA/TFA.
S6
Fig. S4 Normalized absorption spectra of the dye DTP-TP dye recorded in different solvents
Fig. S5 Normalized absorption spectra of the dye DTP-QP dye recorded in different solvents
S7
Fig. S6 Normalized absorption spectra of the dye DTP-QS dye recorded in different solvents
Fig. S7. Absorption spectra of the aldehyde precursors recorded in DCM
S8
Fig. S8 Normalized emission spectra of the dyes recorded in DCM
Fig. S9 Differential pulse voltammograms of the dyes recorded in DCM
S9
Table S1 Comparison between experimental and calculated maximum absorption wavelength in THF solvent
Dye λmaxexp (nm) λmax
cal (nm) λmaxcal − λmax
exp (nm)DTP-TP 478 482 4DTP-TS 497 534 37DTP-QP 453 480 27DTP-QS 517 539 22
Fig. S10 Computed interplanar angles between the different aryl groups in the dyes
S10
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
3.0
3.1
3.2
3.3
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
10.
087
8.
189
8.
168
8.
030
8.
025
8.
013
8.
008
7.
690
7.
671
7.
515
7.
497
7.
260
4.
827
4.
809
4.
790
2.
166
2.
152
2.
148
2.
142
2.
129
1.
607
1.
464
1.
444
1.
426
1.
408
1.
009
0.
990
0.
971
0.
066
1H
2.8
5
1H
2.1
2
1H
2.0
5
1H
1.9
9
1H
1.9
6 1
H 1
.91
1H
1.0
0
1H
0.8
9 1
H 0
.84
Fig. S11 1H NMR spectra of S1 recorded in CDCl3
S11
(tho
usan
dths
)-1
.01.
03.
05.
07.
09.
011
.013
.015
.017
.019
.021
.023
.025
.027
.029
.031
.033
.035
.0
X : parts per Million : Carbon13200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
192
.021
191
.909
142
.648
135
.800
130
.232
129
.600
129
.307
129
.142
125
.801
111
.139
77.
441
77.
122
76.
805
57.
109
32.
285
32.
200
19.
943
13.
636
Fig. S12 13C NMR spectra of S1 recorded in CDCl3
S12
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0
9.
947
8.
115
8.
106
7.
811
7.
802
7.
596
7.
260
4.
831
4.
813
4.
794
2.
193
2.
175
2.
156
2.
137
2.
119
1.
656
1.
464
1.
445
1.
427
1.
409
1.
390
1.
013
0.
994
0.
976
1H
3.0
0
1H
2.1
4
1H
2.0
8
1H
2.0
0
1H
1.9
2
1H
0.9
6
1H
0.9
5
1H
0.9
4
Fig. S13 1H NMR spectra of S2 recorded in CDCl3
S13
abun
danc
e0
0.1
0.2
0.3
0.4
X : parts per Million : Carbon13200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
183
.113
148
.560
144
.326
143
.077
141
.466
137
.242
136
.927
129
.176
128
.480
128
.051
127
.927
124
.523
123
.026
111
.670
77.
479
77.
165
76.
840
57.
161
56.
980 3
2.19
0
19.
929
13.
617
Fig. S14 13C NMR spectra of S2 recorded in CDCl3
S14
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
10.
124
8.
120
8.
101
8.
042
8.
026
8.
022
7.
978
7.
958
7.
691
7.
679
7.
672
7.
663
7.
658
7.
519
7.
515
7.
503
7.
498
7.
400
7.
384
7.
379
7.
322
7.
306
7.
301
7.
260
1.
584
1.
342
1.
303
0.
066
9.09
9.14
3.22
2.20
2.12
2.09
2.08
2.03
1.00
1.00
Fig. S15 1H NMR spectra of S3 recorded in CDCl3
S15
abun
danc
e0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.1
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
X : parts per Million : Carbon13200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
192
.409
153
.289
152
.984
152
.841
152
.755
144
.078
138
.634
135
.612
135
.469
132
.675
131
.569
130
.120
129
.900
129
.767
129
.462
125
.438
125
.343
125
.190
125
.152
125
.076
124
.485
77.
584
77.
432
77.
317
77.
260
77.
117
76.
793
31.
446
31.
351
31.
294
Fig. S16 13C NMR spectra of S3 recorded in CDCl3
S16
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0
9.
988
8.
074
8.
054
7.
987
7.
966
7.
889
7.
879
7.
820
7.
810
7.
681
7.
668
7.
660
7.
647
7.
428
7.
416
7.
406
7.
399
7.
378
7.
260
1.
355
1.
344
1.
318
1H
18.
00
1H
4.0
5
1H
4.0
0 1
H 1
.16
1H
0.8
4
1H
0.8
2
1H
0.8
1 1
H 1
.03
Fig. S17 1H NMR spectra of S4 recorded in CDCl3
S17
(tho
usan
dths
)0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
X : parts per Million : Carbon13200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
183
.513
135
.802
132
.665
130
.153
129
.962
128
.179
127
.507
125
.505
125
.424
77.
422
77.
107
76.
788
31.
341
Fig. S18 13C NMR spectra of S4 recorded in CDCl3
S18
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0
10.
084
8.
316
8.
285
8.
264
8.
035
8.
014
7.
897
7.
877
7.
780
7.
770
7.
762
7.
758
7.
751
7.
688
7.
683
7.
669
7.
663
7.
652
7.
648
7.
417
7.
411
7.
396
7.
381
7.
375
7.
371
7.
360
7.
353
7.
284
7.
270
7.
260
7.
209
7.
195
4.
854
4.
835
4.
817
2.
203
2.
185
2.
167
2.
085
2.
065
2.
044
1.
582
1.
319
1.
294
1.
287
1.
256
1.
163
1.
144
1.
126
1.
107
1.
089
1.
035
1.
033
1.
014
0.
995
0.
762
0.
743
0.
733
0.
724
0.
715
0.
696
1H
10.
20
1H
4.1
4
1H
4.1
1
1H
3.1
5
1H
3.1
5
1H
3.0
5
1H
2.1
5
1H
2.1
3
1H
2.0
4
1H
2.0
2
1H
2.0
0
1H
1.9
0
1H
1.0
3 1
H 1
.02
1H
1.0
0
1H
0.9
6
1H
0.9
2
Fig. S19 1H NMR spectra of 7 recorded in CDCl3
S19
(tho
usan
dths
)0
10.0
20.0
30.0
40.0
X : parts per Million : Carbon13210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
192
.056
152
.726
150
.778
144
.673
143
.360
140
.363
139
.330
138
.752
135
.411
130
.209
129
.195
128
.947
127
.660
127
.345
127
.135
126
.535
125
.556
124
.710
123
.083
121
.869
121
.577
120
.798
119
.787
117
.401
112
.897
112
.360
77.
419
77.
101
76.
933
76.
783
56.
742
55.
407
40.
326
32.
536
32.
212
32.
018
29.
791
29.
679
26.
186
23.
215
23.
072
23.
034
22.
786
19.
989
14.
224
Fig. S20 13C NMR spectra of 7 recorded in CDCl3
S20
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0
9.
944
8.
305
8.
151
8.
141
7.
894
7.
874
7.
821
7.
810
7.
779
7.
769
7.
762
7.
758
7.
750
7.
685
7.
674
7.
669
7.
666
7.
653
7.
649
7.
641
7.
412
7.
397
7.
383
7.
376
7.
373
7.
355
7.
340
7.
286
7.
273
7.
263
7.
260
7.
196
7.
183
4.
857
4.
839
4.
821
2.
234
2.
215
2.
196
2.
177
2.
159
2.
084
2.
063
2.
043
1.
582
1.
512
1.
493
1.
474
1.
455
1.
178
1.
160
1.
142
1.
124
1.
105
1.
087
1.
041
1.
023
1.
004
0.
769
0.
756
0.
751
0.
731
0.
713
0.
694
0.
676
9.94
4.14
4.06
3.13
2.93
2.90
2.15
2.10
2.06
1.78
1.00
0.93
0.91
0.83
0.83
0.81
0.73
Fig. S21 1H NMR spectra of 8 recorded in CDCl3
S21
(tho
usan
dths
)0
10.0
20.0
30.0
40.0
50.0
60.0
X : parts per Million : Carbon13200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
182
.958
152
.619
150
.655
149
.730
144
.839
144
.591
142
.312
142
.121
141
.730
140
.224
139
.251
138
.565
137
.335
137
.125
127
.257
127
.123
127
.085
127
.028
124
.845
124
.444
122
.976
121
.450
121
.307
120
.697
119
.686
117
.999
117
.274
117
.083
113
.003
112
.240
56.
701
55.
290
40.
216
32.
044
26.
076
23.
111
19.
869
13.
891
13.
557
Fig. S22 13C NMR spectra of 8 recorded in CDCl3
S22
abun
danc
e0
0.1
0.2
0.3
0.4
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0
10.
124
8.
255
8.
172
8.
153
8.
040
7.
920
7.
900
7.
828
7.
808
7.
783
7.
765
7.
749
7.
730
7.
718
7.
696
7.
639
7.
556
7.
536
7.
408
7.
392
7.
371
7.
352
7.
332
7.
312
7.
294
7.
280
7.
260
7.
212
7.
199
2.
062
2.
042
2.
022
1.
325
1.
252
1.
187
1.
168
1.
150
1.
132
1.
114
1.
097
0.
742
0.
724
0.
706
10.0
5
9.29
9.20
5.18
4.98
4.18
4.12
4.11
2.18
1.90
1.11
1.02
1.01
1.01
1.00
0.93
0.89
Fig. S23 1H NMR spectra of 9 recorded in CDCl3
S23
(tho
usan
dths
)0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
X : parts per Million : Carbon13190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
192
.466
152
.473
150
.880
144
.513
138
.811
138
.647
137
.330
137
.210
135
.982
135
.783
135
.213
133
.762
131
.575
130
.551
130
.503
130
.358
130
.135
129
.958
129
.727
129
.445
129
.149
127
.420
127
.343
127
.105
126
.893
126
.428
126
.140
125
.877
125
.400
125
.299
124
.925
124
.540
123
.066
121
.642
120
.806
119
.872
117
.652
112
.643
55.
350
40.
273
31.
322
29.
805
26.
199
23.
201
14.
141
14.
006
Fig. S24 13C NMR spectra of 9 recorded in CDCl3
S24
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
9.
982 8.
249
8.
105
7.
916
7.
906
7.
896
7.
822
7.
812
7.
785
7.
768
7.
726
7.
722
7.
712
7.
705
7.
695
7.
691
7.
671
7.
627
7.
622
7.
433
7.
412
7.
394
7.
386
7.
381
7.
375
7.
370
7.
365
7.
298
7.
285
7.
260
7.
197
7.
184
2.
061
2.
047
2.
041
2.
034
2.
020
1.
579
1.
362
1.
324
1.
255
1.
170
1.
152
1.
134
1.
115
0.
765
0.
746
0.
728
0.
709
10.0
0
9.12
9.08
8.07
4.27
4.14
4.03
2.12
1.85
1.00
0.98
0.93
0.89
0.87
0.86
0.85
Fig. S25 1H NMR spectra of 10 recorded in CDCl3
S25
(tho
usan
dths
)0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
X : parts per Million : Carbon13200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
183
.509
152
.779
152
.721
152
.574
150
.877
148
.836
144
.903
144
.784
144
.498
140
.288
139
.378
138
.725
137
.256
137
.056
135
.912
135
.616
135
.564
134
.110
130
.196
130
.144
128
.880
127
.979
127
.355
127
.107
126
.902
125
.820
125
.596
125
.453
125
.376
125
.171
125
.138
124
.842
123
.069
121
.672
121
.000
120
.804
119
.889
117
.677
117
.300
112
.843
112
.199
55.
359
40.
252
34.
907
31.
370
29.
787
26.
198
23.
189
14.
213
Fig. S26 13C NMR spectra of 10 recorded in CDCl3
S26
abun
danc
e0
0.1
0.2
0.3
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
8.
336
8.
313
8.
288
8.
155
8.
134
8.
044
8.
024
7.
887
7.
869
7.
837
7.
815
7.
709
7.
688
7.
583
7.
570
7.
493
7.
477
7.
474
7.
394
7.
376
7.
363
7.
349
7.
332
7.
262
7.
248
4.
856
4.
838
4.
821
2.
494
2.
490
2.
486
2.
172
2.
151
2.
144
2.
124
2.
113
2.
092
2.
074
2.
055
2.
038
2.
020
1.
399
1.
380
1.
361
1.
343
1.
324
1.
306
1.
092
1.
074
1.
056
1.
037
1.
019
1.
001
0.
918
0.
900
0.
881
0.
862
0.
637
0.
619
0.
600
0.
580
0.
563
0.
532
10.0
0
6.07
4.09
3.92
3.79
2.79
2.10
1.92
1.87
1.85
1.00
0.96
0.84
0.80
0.80
Fig. S27 1H NMR spectra of DTP-TP recorded in DMSO-d6
S27
(tho
usan
dths
)0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
X : parts per Million : Carbon13170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
163
.837
152
.793
150
.826
144
.854
144
.171
142
.909
141
.796
140
.881
140
.334
139
.362
138
.367
137
.121
131
.531
131
.464
129
.014
127
.920
127
.647
127
.053
127
.021
125
.848
123
.493
122
.365
121
.818
120
.515
117
.903
117
.448
117
.029
112
.999
112
.926
56.
659
55.
540
55.
435
32.
066
26.
444
22.
986
22.
595
19.
840
14.
322
13.
874
Fig. S28 13C NMR spectra of DTP-TP recorded in DMSO-d6
S28
abun
danc
e0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.1
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.2
0.21
0.22
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
8.
400
8.
259
8.
236
8.
233
8.
162
8.
152
8.
142
8.
038
8.
026
8.
018
8.
010
7.
986
7.
976
7.
883
7.
866
7.
847
7.
827
7.
804
7.
771
7.
752
7.
735
7.
690
7.
674
7.
573
7.
560
7.
488
7.
473
7.
375
7.
363
7.
350
7.
328
7.
302
7.
270
7.
231
7.
218
4.
825
4.
809
3.
391
2.
490
2.
453
2.
144
2.
123
2.
107
2.
082
2.
069
2.
052
2.
041
2.
019
1.
394
1.
375
1.
357
1.
339
1.
070
1.
052
1.
034
1.
016
0.
931
0.
913
0.
894
0.
632
0.
614
0.
596
0.
571
0.
441
0.
417
0.
398
9.80
6.19
4.16
4.034.18
3.10
2.13
2.08
2.06
1.10
1.05
1.01
0.96
0.91
Fig. S29 1H NMR spectra of DTP-TS recorded in DMSO-d6
S29
(tho
usan
dths
)0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
X : parts per Million : Carbon13180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
164
.163
152
.769
152
.495
150
.810
145
.687
145
.003
144
.174
141
.688
141
.278
140
.329
139
.344
138
.327
136
.920
136
.255
127
.912
127
.636
127
.231
126
.296
124
.959
123
.479
122
.120
121
.984
121
.791
121
.653
121
.038
120
.497
118
.197
117
.591
117
.415
117
.003
113
.184
112
.845
79.
691
56.
706
55.
533
31.
716
26.
436
22.
996
19.
855
14.
337
13.
874
Fig. S30 13C NMR spectra of DTP-TS recorded in DMSO-d6
S30
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
8.
368
8.
331
8.
153
8.
128
8.
107
8.
038
8.
018
7.
981
7.
959
7.
939
7.
894
7.
878
7.
810
7.
791
7.
751
7.
673
7.
654
7.
594
7.
581
7.
535
7.
514
7.
476
7.
460
7.
457
7.
388
7.
375
7.
366
7.
347
7.
329
7.
300
7.
284
7.
263
7.
248
7.
229
7.
217
2.
499
2.
495
2.
490
2.
485
2.
481
2.
141
2.
101
2.
081
2.
070
2.
007
1.
986
1.
979
1.
947
1.
221
1.
147
1.
078
1.
060
1.
042
1.
024
1.
005
0.
988
0.
649
0.
632
0.
613
0.
595
0.
576
0.
558
0.
539
10.0
1
9.09
9.08
5.03
4.13
4.04
3.06
2.01
2.00
2.00
1.96
1.01
0.99
0.99
0.97
0.97
0.92
0.91
0.90
0.81
Fig. S31 1H NMR spectra of DTP-QP recorded in DMSO-d6
S31
(tho
usan
dths
)0
1.0
2.0
3.0
4.0
5.0
X : parts per Million : Carbon13170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
163
.872
154
.137
152
.783
152
.314
152
.200
152
.076
151
.367
150
.959
144
.763
144
.075
142
.652
140
.259
139
.269
138
.766
138
.358
138
.224
136
.762
136
.670
136
.252
135
.814
132
.782
131
.842
131
.100
130
.667
130
.177
129
.826
127
.894
127
.566
126
.744
126
.693
125
.480
125
.410
123
.459
121
.882
121
.680
120
.555
119
.716
117
.671
116
.964
116
.922
113
.797
112
.809
112
.765
55.
464
34.
938
31.
597
26.
414
22.
972 1
4.28
4
Fig. S32 13C NMR spectra of DTP-QP recorded in DMSO-d6
S32
abun
danc
e0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.1
0.11
0.12
0.13
0.14
0.15
X : parts per Million : Proton10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0
8.
660
8.
498
8.
480
8.
369
8.
350
8.
012
7.
962
7.
940
7.
900
7.
885
7.
815
7.
801
7.
764
7.
717
7.
696
7.
680
7.
659
7.
633
7.
591
7.
570
7.
493
7.
481
7.
434
7.
418
7.
260
2.
145
2.
073
1.
377
1.
373
1.
217
1.
157
1.
142
1.
124
0.
886
0.
738
0.
721
18.2
3
11.0
0
10.0
0
4.03
4.00
3.79
3.73
1.87
0.93
0.84
Fig. S33 1H NMR spectra of DTP-QS recorded in CDCl3
S33
(tho
usan
dths
)0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
X : parts per Million : Carbon13180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
152
.981
150
.569
150
.257
150
.164
146
.383
130
.053
129
.938
129
.793
129
.626
129
.524
129
.464
129
.333
127
.524
127
.357
127
.123
126
.975
126
.546
126
.353
122
.892
122
.351
121
.569
120
.640
119
.674
117
.646
114
.833
112
.204
55.
199 3
9.86
3
35.
186
34.
964
30.
722
30.
374
25.
883
22.
732
13.
435
13.
373
Fig. S34 13C NMR spectra of DTP-QS recorded in CDCl3 with small amount of TFA
S34