Supplementary Information for:
A rare case for binding a diquat salt by two cyclo[6]aramides
Min Xu, Long Chen, Yiming Jia, Lijun Mao, Yi Ren, Wen Feng, Lihua Yuan*
College of Chemistry, Key Laboratory for Radiation Physics and Technology of Ministry of Education, Institute of
Nuclear Science and Technology, Sichuan University, Chengdu 610064, China.
29 Wangjiang Road, Sichuan University, Chengdu 610064, China; Email: lhyuan@scu.edu.cn
Table of Contents
1. Chemical structures ......................................................................................................................... S2
2. 2D NOESY experiment .................................................................................................................. S2
3. Job’s plot of 1•2 by UV-vis method................................................................................................ S3
4. Binding constant of 1•2 by UV-vis method .................................................................................... S3
5. Binding constant of 1•3 by UV-vis method .................................................................................... S4
6. Job’s plot of 1•3 by UV-vis method................................................................................................ S4
7. Molecular modeling of 1•2 ............................................................................................................. S4
S1
1. Chemical structures
Figure S1. Chemical structures of cyclo[6]aramide 1 and guest molecules 2 and 3 (1).
2. 2D NOESY experiment
S2
Figure S2. 2D NOESY spectrum (600 MHz, CD3COCD3, 298 K, mixing time = 0.5 s) of a mixture of 10
mM 1 and 5.0 mM 2.
3. Job’s plot of 1•2 by UV-vis method
A series of solutions containing 1 and 2 were prepared such that the sum of the total concentration of 2 and 1
remained constant (50 μM). The mole fraction of 2 was varied from 0 to 1.0.
Figure S3. (a) The UV-vis spectra of 1 with different concentration. (b) The UV-vis spectra of 1 and
diquat 2 with different concentration ratio. (c) Job’s plot for the determination of stoichiometry in the
complex formed by 1 and diquat 2 from absorbance measurements in acetone.
4. Binding constant of 1•2 by UV-vis method
Figure S4. (a) Titration curves of 1 (2.0 × 10-5 M) upon addition of 2 at 0, 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 ×10-5 M in acetone. (b) Non-linear curve fitting
of 1 with concentration of 2 at 350 nm in acetone.
S3
5. Binding constant of 1•3 by UV-vis method
Fig. S5 (a) Titration curves of 1 (5.0 × 10-5 M) upon addition of 3 from 0 to 1.0 ×10-4 M in acetone. (b)
Non-linear curve fitting of 1 with concentration of 3 at 350 nm in acetone.
6. Job’s plot of 1•3 by UV-vis method
Figure S6. (a) The UV-vis spectra of 1 with different concentration. (b) The UV-vis spectra of 1 and guest
3 with different concentration ratio. (c) Job’s plot for the determination of stoichiometry in the complex
formed by 1 and guest 3 from absorbance measurements in acetone.
7. Molecular modeling of 1•2
All the calculations were carried out by utilizing the Gaussian 09 program package. The geometry optimizations
were performed at the density functional theory (DFT) level. The ONIOM (B3PW91/6-31G(d):PM6) basic from the
Gaussian basis set library has been used in all the structural optimizations.
Table S1. Atomic coordinates for the optimized structure of the complex 1•2（2）
-Standard orientation:
---------------------------------------------------------------------
S4
Center
Atomic
Number
Atomic
Number
Coordinates (Angstroms)
Type
X
Y
Z
--------------------------------------------------------------------1
6
0
8.213092 -3.173537 -1.807714
2
6
0
9.570581 -3.566218 -1.970460
3
6
0
7.921998 -1.819162 -1.593764
4
7
0
7.187727 -4.164906 -1.930508
5
6
0
10.605942 -2.627507 -1.928033
6
8
0
9.734088 -4.919884 -2.175001
7
6
0
8.937070 -0.856075 -1.564375
8
1
0
6.870672 -1.506547 -1.444445
9
6
0
5.883111 -3.995606 -1.456005
10
1
0
7.479957 -5.061832 -2.341111
11
1
0
11.638176 -2.939091 -2.045043
12
6
0
10.287037 -1.282912 -1.726654
13
6
0
11.070751 -5.404675 -2.456405
14
7
0
8.686079
15
6
0
4.857907 -5.014559 -1.844776
16
8
0
5.541569 -3.013445 -0.807299
17
8
0
11.202780 -0.252534 -1.663567
18
1
0
11.723958 -5.231955 -1.595633
19
1
0
11.459843 -4.942618 -3.368760
20
1
0
10.892030 -6.477609 -2.603967
21
6
0
7.427419
1.121465 -1.228756
22
1
0
9.525654
1.143709 -1.445196
23
6
0
5.068496 -6.388705 -2.097693
24
6
0
3.546877 -4.522678 -1.926548
25
6
0
12.596012 -0.567559 -1.906278
S5
0.545329 -1.410701
26
6
0
7.336117
2.616104 -1.183686
27
8
0
6.395737
0.460556 -1.140654
28
6
0
4.001931 -7.245001 -2.404909
29
8
0
6.371332 -6.779701 -2.011290
30
6
0
2.453028 -5.331493 -2.257749
31
1
0
3.368171 -3.451618 -1.724702
32
1
0
13.065107
33
1
0
12.722846 -0.984660 -2.909876
34
1
0
12.971256 -1.240683 -1.129736
35
6
0
8.369013
3.548503 -0.925597
36
6
0
6.043837
3.117457 -1.392360
37
6
0
2.708971 -6.708026 -2.476283
38
1
0
4.174684 -8.299433 -2.580509
39
6
0
1.132772 -4.617045 -2.334675
40
6
0
8.114013
4.926418 -0.871661
41
8
0
9.596230
2.993112 -0.729739
42
6
0
5.742329
4.485134 -1.368322
43
1
0
5.225095
2.399566 -1.583873
44
8
0
1.599059 -7.452169 -2.752037
45
7
0
0.151476 -5.219217 -3.132233
46
8
0
0.964809 -3.535092 -1.783255
47
1
0
8.913731
5.626988 -0.663027
48
6
0
6.806008
5.379048 -1.088243
49
6
0
4.307272
4.816962 -1.645793
50
6
0
-1.116791 -4.654426 -3.472354
51
1
0
0.287117 -6.186830 -3.465511
52
8
0
6.442295
6.691653 -1.039446
53
7
0
4.043982
6.115394 -2.090904
S6
0.421811 -1.830394
54
8
0
3.439362
55
6
0
-2.136751 -5.550571 -3.903609
56
6
0
-1.369936 -3.275090 -3.492726
57
6
0
2.796501
6.611391 -2.583207
58
1
0
4.806402
6.814159 -2.091202
59
6
0
-3.371908 -5.088209 -4.360837
60
8
0
-1.774081 -6.881471 -3.829875
61
6
0
-2.584259 -2.786672 -3.993458
62
1
0
-0.610016 -2.572404 -3.113107
63
6
0
2.711838
7.998182 -2.908039
64
6
0
1.682948
5.798485 -2.816234
65
6
0
-3.588240 -3.710017 -4.405418
66
1
0
-4.145133 -5.782159 -4.670152
67
6
0
-2.640194 -7.849256 -4.471995
68
7
0
-2.845311 -1.394238 -4.207880
69
6
0
1.557257
8.547171 -3.468033
70
8
0
3.861110
8.704985 -2.619929
71
6
0
0.519520
6.322892 -3.398796
72
1
0
1.725027
4.730619 -2.536443
73
8
0
-4.734931 -3.105941 -4.876677
74
1
0
-3.604622 -7.889665 -3.957407
75
1
0
-2.079684 -8.781316 -4.329975
76
1
0
-2.752410 -7.616599 -5.535300
77
6
0
-2.288955 -0.343765 -3.477017
78
1
0
-3.607796 -1.201971 -4.880093
79
1
0
1.503691
9.604874 -3.701380
80
6
0
0.467235
7.707354 -3.715913
81
6
0
3.932890 10.085598 -3.050126
S7
3.952468 -1.530050
82
7
0
-0.596335
83
6
0
-5.866717 -3.955535 -5.187736
84
6
0
-2.644459
85
8
0
-1.493240 -0.517313 -2.553740
86
8
0
-0.726056
87
1
0
3.182437 10.682879 -2.525589
88
1
0
3.825547 10.151814 -4.136511
89
1
0
4.947092 10.364541 -2.737134
90
6
0
-0.852517
4.263663 -3.154015
91
1
0
-1.256971
5.898543 -4.429082
92
1
0
-6.172246 -4.519749 -4.300896
93
1
0
-5.627689 -4.608232 -6.031789
94
1
0
-6.630681 -3.217135 -5.461562
95
6
0
-3.772944
1.484015 -4.643567
96
6
0
-1.749343
2.030924 -3.465239
97
6
0
-0.840694
9.471510 -4.737509
98
6
0
-1.915699
3.395228 -3.742087
99
8
0
-0.180606
3.835085 -2.216284
100
6
0
-3.982826
2.838080 -4.944109
101
8
0
-4.612671
0.483196 -5.023194
102
1
0
-0.871256
1.715219 -2.867623
103
1
0
-0.760151 10.157896 -3.889280
104
1
0
-1.855580
9.483209 -5.155876
105
1
0
-0.094843
9.680817 -5.510296
106
6
0
-3.049144
3.782105 -4.493998
107
1
0
-4.850921
3.147880 -5.513212
108
8
0
-3.136358
5.122062 -4.724739
109
6
0
7.455643
7.711225 -0.825831
S8
5.496860 -3.749745
1.050603 -3.902512
8.099720 -4.283574
110
1
0
7.920722
7.579585
111
1
0
8.185723
7.693802 -1.640555
112
1
0
6.848350
8.627934 -0.855172
113
6
0
10.744192
3.852715 -0.492417
114
1
0
10.917206
4.497159 -1.359466
115
1
0
10.604867
4.421223
116
1
0
11.549408
3.111231 -0.381428
117
6
0
6.716589 -8.168952 -2.259203
118
1
0
6.230222 -8.815571 -1.523367
119
1
0
6.464358 -8.441918 -3.287997
120
1
0
7.806102 -8.151471 -2.108529
121
6
0
1.742276 -8.864566 -3.058634
122
1
0
2.351197 -8.995635 -3.958323
123
1
0
2.153366 -9.396941 -2.196121
124
1
0
0.697114 -9.152984 -3.240866
125
6
0
-5.816744
0.796959 -5.773354
126
1
0
-6.472384
1.439568 -5.178757
127
1
0
-5.554626
1.240690 -6.738121
128
1
0
-6.255838 -0.203714 -5.901291
129
6
0
-4.266058
5.643372 -5.475659
130
1
0
-4.257608
5.243051 -6.493884
131
1
0
-5.199984
5.427269 -4.948758
132
1
0
-4.050934
6.721790 -5.470945
133
6
0
1.580376 -4.637836
4.201809
134
6
0
2.546926 -5.399689
4.920402
135
6
0
1.677844 -3.239826
4.208574
136
7
0
0.501451 -5.346877
3.587915
137
6
0
3.568468 -4.783829
5.645680
S9
0.155452
0.431571
138
8
0
2.355298 -6.763327
4.828432
139
6
0
2.674242 -2.598732
4.957427
140
1
0
0.958908 -2.637879
3.627759
141
6
0
-0.351148 -4.841775
2.599677
142
1
0
0.396865 -6.324686
3.902334
143
1
0
4.305510 -5.376011
6.176951
144
6
0
3.624649 -3.388422
5.665315
145
6
0
3.160524 -7.615956
5.679829
146
7
0
2.732237 -1.178314
5.120552
147
6
0
-1.565890 -5.660862
2.282160
148
8
0
-0.166633 -3.751836
2.065634
149
8
0
4.555180 -2.642746
6.357828
150
1
0
3.000739 -7.365199
6.732869
151
1
0
4.214578 -7.544526
5.395152
152
1
0
2.757738 -8.609542
5.445883
153
6
0
2.201487 -0.243808
4.227684
154
1
0
3.287929 -0.855953
5.926873
155
6
0
-1.711205 -7.062949
2.422586
156
6
0
-2.667173 -4.943819
1.797342
157
6
0
5.503051 -3.352456
7.193556
158
6
0
2.223279
1.192054
4.656087
159
8
0
1.683017 -0.558815
3.159639
160
6
0
-2.911972 -7.715825
2.116723
161
8
0
-0.592555 -7.702447
2.871020
162
6
0
-3.898648 -5.549075
1.499249
163
1
0
-2.564978 -3.853227
1.651798
164
1
0
6.079227 -2.525460
7.627870
165
1
0
6.142595 -3.993141
6.578559
S10
166
1
0
4.978676 -3.916644
7.970572
167
6
0
3.187320
1.827869
5.475502
168
6
0
1.190667
1.977171
4.133498
169
6
0
-3.995243 -6.950901
1.660722
170
1
0
-3.001644 -8.789475
2.225604
171
6
0
-4.960518 -4.600237
1.031259
172
6
0
3.123119
3.200181
5.751417
173
8
0
4.154444
0.993678
5.947764
174
6
0
1.082531
3.352916
4.383255
175
1
0
0.432768
1.494068
3.491853
176
8
0
-5.208643 -7.478209
1.331895
177
7
0
-6.290244 -5.037400
1.042798
178
8
0
-4.656087 -3.461980
0.697192
179
1
0
3.870622
3.673062
6.376533
180
6
0
2.072528
3.948737
5.201361
181
6
0
-0.074168
4.015451
3.700768
182
6
0
-7.418239 -4.210831
0.738542
183
1
0
-6.515461 -6.016887
1.270408
184
8
0
1.913696
5.288229
5.391469
185
7
0
-0.512289
5.237593
4.210758
186
8
0
-0.622176
3.450318
2.754857
187
6
0
-8.691487 -4.834100
0.607648
188
6
0
-7.333870 -2.818616
0.603840
189
6
0
-1.640848
5.974228
3.729100
190
1
0
0.030452
5.711209
4.949762
191
6
0
-9.845019 -4.086378
0.358454
192
8
0
-8.654889 -6.208353
0.742274
193
6
0
-8.476841 -2.042484
0.375041
S11
194
1
0
-6.343332 -2.320946
0.683227
195
6
0
-1.749701
7.346010
4.095329
196
6
0
-2.662871
5.391871
2.968997
197
6
0
-9.734194 -2.698966
0.245460
198
1
0
-10.807201 -4.574605
0.250735
199
6
0
-9.919535 -6.911699
0.813534
200
7
0
-8.454960 -0.613683
0.292158
201
6
0
-2.858013
8.110945
3.724531
202
8
0
-0.680571
7.807620
4.834927
203
6
0
-3.797192
6.130447
2.607239
204
1
0
-2.571051
4.335466
2.653702
205
8
0
-10.786061 -1.838914 -0.003835
206
1
0
-10.514781 -6.544185
1.654884
207
1
0
-9.592372 -7.944924
0.985235
208
1
0
209
6
0
-7.305574
0.176027
0.394429
210
1
0
-9.379488 -0.171020
0.180728
211
1
0
-2.924878
9.157842
3.999241
212
6
0
-3.874679
7.501366
2.985977
213
6
0
-0.755160
9.154805
5.363166
214
7
0
-4.920951
5.557179
1.932312
215
6
0
-12.125715 -2.390511
0.001941
216
6
0
-7.471594
1.666563
0.410850
217
8
0
-6.182855 -0.308230
0.497596
218
8
0
-5.028228
8.128042
2.561132
219
1
0
-1.617419
9.256268
6.028990
220
1
0
-0.779140
9.879964
4.544273
221
1
0
0.185552
9.226928
5.923701
-10.453431 -6.822997 -0.137192
S12
222
6
0
-4.933967
4.297190
1.329032
223
1
0
-5.764622
6.150067
1.907905
224
1
0
-12.347845 -2.843568
0.973058
225
1
0
-12.243975 -3.102109 -0.820666
226
1
0
-12.737617 -1.494545 -0.162439
227
6
0
-8.623480
2.433290
0.114428
228
6
0
-6.309973
2.362418
0.775429
229
6
0
-5.271502
9.480179
3.021742
230
6
0
-6.257811
3.758187
0.883913
231
8
0
-3.922357
3.610157
1.219143
232
6
0
-8.615229
3.834246
0.189844
233
8
0
-9.711982
1.703770 -0.257844
234
1
0
-5.391457
1.777858
0.990503
235
1
0
-5.319881
9.508020
4.114389
236
1
0
-6.252512
9.694100
2.578692
237
1
0
-4.507798 10.156054
2.625927
238
6
0
-7.434679
4.482188
0.576763
239
1
0
-9.506022
4.404082 -0.044709
240
8
0
-7.305737
5.835427
0.679540
241
6
0
2.862897
6.013409
6.218991
242
1
0
2.831329
5.636777
7.245701
243
1
0
3.864145
5.955637
5.782127
244
1
0
2.464233
7.036729
6.158073
245
6
0
5.210916
1.527634
6.790819
246
1
0
5.788764
2.276835
6.241842
247
1
0
4.788386
1.921813
7.719587
248
1
0
5.812988
0.626093
6.978013
249
6
0
-0.638122 -9.133413
3.116834
S13
250
1
0
-1.374294 -9.359340
3.894181
251
1
0
-0.838218 -9.669359
2.184672
252
1
0
0.385247 -9.324613
3.470900
253
6
0
-5.450547 -8.897709
1.524077
254
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0
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255
1
0
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256
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0
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257
6
0
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258
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0
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0
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270
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S14
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1.273709 -1.127605
2.327315
1.198916
--------------------------------------------------------------------References
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