Supporting Information
Fluorescent coumarin derivatives with viscosity sensitive emission - synthesis,
photophysical properties and computational studies
Kiran R. Phatangare, Sandip K. Lanke, Nagaiyan Sekar*
Department of Intermediate and Dyestuff Technology
Institute of Chemical Technology (Formerly UDCT),
N. P. Marg, Matunga, Mumbai - 400 019.
Maharashtra, India.
Email: n.sekar@ictmumbai.edu.in, nethi.sekar@gmail.com
Table of Contents:
SI-Table 1 Observed UV-visible absorption and vertical excitation of coumarin 4 in
different solvents. …………………………………………………………………
2-3
SI-Table 2 Observed UV-visible absorption, excitation and vertical excitation of
coumarin 5 in different solvents……………………………………………………
3-4
SI-Table 3 Observed UV-visible absorption and vertical excitation of coumarin 6 in
different solvents. ………………………………………………………………….
4-5
SI-Table 4 Observed UV-visible absorption and vertical excitation of
coumarin 7 in different solvents………………………………………………….....
6-7
SI-Table 5 Thermal Gravimetric Analysis (TGA) of compound 4-7……………….
7
SI-Table 6 Synthesis of benzazolyl-benzo[f]chromen-3-one from
3-(1,3-benzazol-2- yl)naphthalen-2-ol ………………………………………………
8
1H NMR and Mass Spectra ………………………………………………………..
9-13
Cartesian Coordinates ………………………………………………………………
14-18
1
SI-Table 1. Observed UV-visible absorption and vertical excitation of compound 4 in different
solvents.a
Experimentalb
TD-DFTc
Exc
Abs
Molar
Vertical
λ
Solvent
λ
absorptivity
Excitation
(nm)
f
Assignment
(nm) (a)
nm
eV
306
4.0580 0.4425
H→L+1 (65%)d
L mol-1 cm-1
314
37932.0
329
36624.0
349
3.5503 0.1795
H-1→L (66%)e
314
40548.0
306
4.0557 0.4489
H→L+1 (65%)d
329
36297.0
350
3.5472 0.1829
H-1→L (66%)e
317
36951.0
274
306
4.0564 0.4465
H→L+1 (65%)d
329
37278.0
308
349
3.5502 0.1815
H-1→L (66%)e
320
35610.3
282
306
4.0489 0.4642
H→L+1 (66%)d
329
30672.6
303
350
3.5472 0.1917
H-1→L (66%)e
317
30378.3
340
306
4.0564 0.4473
H→L+1 (65%)d
317
39567.0
270
306
4.0536 0.4515
H→L+1 (65%)d
332
39567.0
352
351
3.5312 0.1856
H-1→L (67%)e
317
37932.0
306
4.0524 0.3020
H→L+1 (55%)d
353
3.5133 0.1796
H-1→L (67%)e
271
MeOH
268
EtOH
ACN
DMF
Acetone
DCM
273
CHCl3
329
32373.0
317
40875.0
274
306
4.0584 0.3724
H→L+1 (61%)d
332
34989.0
307
352
3.5233 0.1752
H-1→L (67%)e
EtOAc
2
317
41202.0
332
36951.0
4.0557 0.4358
H→L+1 (61%)d
351
3.5278 0.1817
H-1→L (67%)e
376
THF
a
306
Analysis were carried out at room temperature (25 ºC); b Experimentally observed λmax; c TD-
DFT computations were carried out with the use of optimized structures at B3LYP method with
6-31G(d) basis set;d Only major contributions are presented from excited state 3; e Only major
contributions are presented from excited state 2; f = Oscillator strength.
SI-Table 2: Observed UV-visible absorption, excitation and vertical excitation of compound 5 in
different solvents.a
Exptb
Solvent
TD-DFTc
Exc
Abs
Molar
λ
absorptivity λ
(nm) (a)
Vertical
Excitation
f
Assignment
(nm)
nm
eV
L mol-1 cm-1
317
27058.0
274
309
4.0065
0.5981
H→L+1 (66%)d
332
25754.0
324
351
3.5310
0.1573
H-1→L (58%)e
320
24450.0
276
310
4.0022
0.6068
H→L+1 (66%)d
335
23472.0
324
351
3.5291
0.1609
H-1→L (57%)e
317
23080.8
310
4.0049
0.6019
H→L+1 (66%)d
351
3.5299
0.1589
H-1→L (59%)e
MeOH
EtOH
332
ACN
332
27058.0
320
21168.0
284
310
3.9958
0.6217
H→L+1 (66%)d
332
22820.0
305
352
3.5244
0.1677
H-1→L (60%)e
DMF
3
Acetone
335
16691.2
343
351
3.5294
0.1608
H-1→L (56%)e
320
17930.0
277
311
3.9904
0.6251
H→L+1 (66%)d
332
21516.0
327
352
3.5264
0.1662
H-2→L (56%)e
320
28036.0
311
3.9811
0.6335
H→L+1 (67%)d
332
29014.0
351
3.5352
0.1210
H-1→L (64%)*
317
26080.0
279
311
3.9920
0.6151
H→L+1 (66%)d
335
23472.0
326
351
3.5295
0.1395
H-2→L (67%)e
332
27058.0
327
351
3.5278
0.1605
H-2→L (62%)e
DCM
274
CHCl3
EtOAc
THF
a
Analysis were carried out at room temperature (25 ºC); b Experimentally observed λmax;
c
TD-DFT computations were carried out with the use of optimized structures at B3LYP method
with 6-31G(d) basis set;
d
Only major contributions from excited state 4 are presented; e Only
major contributions from excited state 2 are presented; f = Oscillator strength.
*
Only major
contributions from excited state 3 are presented; f = Oscillator strength.
SI-Table 3: Observed UV-visible absorption and vertical excitation of compound 6 in different
solvents.a
Exptb
Solvent
TD-DFTc
Abs
Molar
Exc
Vertical
λ
absorptivity
λ
Excitation
(nm) (a)
f
Assignment
0.5090
H→L+1 (66%)d
(nm)
nm
eV
313
3.9634
L mol-1 cm-1
MeOH
317
26605.0
284
4
332
22536.0
357
3.4741
0.1370
H-1→L (67%) e
317
25666.0
313
3.9608
0.5152
H→L+1 (67%)d
329
20658.0
357
3.4722
0.1404
H-1→L (67%) e
329
18154.0
357
3.4737
0.1391
H-1→L (67%) e
317
20814.5
314
3.9528
0.5288
H→L+1 (67%)d
335
13146.0
357
3.4707
0.1496
H-1→L (67%) e
335
19719.0
343
357
3.4717
0.1395
H-1→L (67%) e
317
37560.0
292
313
3.9601
0.5232
H→L+1 (67%)d
332
33178.0
347
358
3.4654
0.1439
H-1→L (67%) e
317
23162.0
313
3.9646
0.5181
H→L+1 (67%)d
332
19093.0
358
3.4599
0.1434
H-1→L (67%) e
317
38499.0
312
3.9688
0.5065
H→L+1 (66%)d
284
EtOH
ACN
293
DMF
Acetone
336
DCM
285
CHCl3
285
EtOAc
332
32865.0
358
3.4647
0.1361
H-1→L (67%) e
317
50393.0
313
3.9635
0.5177
H→L+1 (67%)d
358
3.4649
0.1408
H-1→L (67%)e
306
THF
329
37873.0
a
Analysis were carried out at room temperature (25 C); b Experimentally observed λmax;
c
TD-DFT computations were carried out with the use of optimized structures at B3LYP method
with 6-31G(d) basis set; d Only major contributions are from excited state 3 are presented; e Only
major contributions are from excited state 2 are presented; f = oscillator strength.
5
SI-Table 4: Observed UV-visible absorption and vertical excitation of compound 7 in different
solvents.a
Exptb
Solvent
TD-DFTc
Exi
Abs
Molar
λ
absorptivity λ
Vertical
Excitation
f
(nm) (a)
Assignment
(nm)
nm
eV
L mol-1 cm-1
321
12480.0
276
314
3.9538 0.5815
H→L+1 (67%)d
336
19032.0
343
353
3.5163 0.1521
H-2→L (49%)e
315
20592.0
276
314
3.9491 0.5900
H→L+1 (67%)d
330
19032.0
331
353
3.5142 0.1554
H-2→L (53%)e
318
17160.0
314
3.9523 0.5855
H→L+1 (67%)d
330
23088.0
353
3.5152 0.1541
H-2→L (48%)e
318
19344.0
308
314
3.9432 0.6063
H→L+1 (67%)d
333
20592.0
354
353
3.5098 0.1637
H-1→L (48%)e
321
21996.0
314
3.9485 0.5894
H→L+1 (67%)d
339
23712.0
353
3.5145 0.1544
H-2→L (56%)e
318
20904.0
308
315
3.9351 0.6050
H→L+1 (67%)d
333
21840.0
343
353
3.5101 0.1440
H-2→L (67%)e
321
42432.0
275
316
3.9229 0.6074
H→L+1 (68%)d
351
23400.0
331
353
3.5143 0.1841
H-2→L (60%)*
318
22152.0
280
315
3.9350 0.5912
H→L+1 (67%)d
MeOH
EtOH
343
ACN
DMF
348
Acetone
DCM
CHCl3
EtOAc
6
330
19188.0
304
352
3.5204 0.1606
H-2→L (49%)*
324
40809.6
310
315
3.9348 0.6001
H→L+1 (67%)d
348
19156.8
350
353
3.5097 0.1066
H-2→L (65%)e
THF
a
Analysis were carried out at room temperature (25 C); b Experimentally observed λmax;
c
TD-DFT computations were carried out with the use of optimized structures at B3LYP method
with 6-31G(d) basis set;
d
Only major contributions from excited state 4 are presented; e Only
major contributions from excited state 2 are presented; * Only major contributions from excited
state 3 are presented; f = Oscillator strength.
SI-Table 5: Thermal Gravimetric Analysis (TGA) of compound 4-7.a
a
Compound
TGA (ºC)
4
302 (91.43%)
5
311 (86.67%)
6
337 (96.32%)
7
323 (94.88%)
TGA was measured in ºC and measure up to 600 ºC.
7
Table SI 6: Synthesis of benzazolyl-benzo[f]chromen-3-one from 3-(1,3-benzazol-2yl)naphthalen-2-ol 3 a
Mp
Phenolic component 1
Ester/ Acid 2
Product
Time
Yield b
(˚C)
Me
O
OH
O
O
O
O
O
OEt
N
24 h
71
> 300
22 h
65
> 300
22 h
66
N
4
Me
OH
H
N
O
O
O
O
H
N
OEt
N
N
5
H
O
OH
COOH
O
292-
O
N
O
HO
6
N
H
OH
H
N
N
O
COOH
O
H
N
HO
23 h
68
> 300
COOH
7
a
295
COOH
N
Reaction condition: starting compound 1 (0.005 mol), starting compound 2 (0.005 mol), H2SO4
(3 mL), room temperature.b Yield: isolated.
8
1H-NMR
of compound 4
9
1H-NMR
of compound 5
10
1H-NMR
of compound 6 (Expansion)
11
1H-NMR
compound 6
12
Mass of compound 7
M+ ion peak
13
Cartesian Coordinates: Compound 4 (Gas Phase)
B3LYP optimized structure
Energy (RB3LYP) = -1088.51012852 a.u.
----------------------------------------------------------------Center
Y
Atomic
Atomic
Coordinates (Angstroms) Number
Number
Type
X
Z
----------------------------------------------------------------1
6
0
-4.766673 -2.152655
0.240563
2
6
0
-3.958506 -3.301784
0.132736
3
6
0
-2.597697 -3.145408
0.019085
4
6
0
-2.005688 -1.854873 -0.007803
5
6
0
-2.820152 -0.673389
0.055146
6
6
0
-4.218256 -0.885137
0.204936
7
6
0
-0.598775 -1.746607 -0.061029
8
6
0
0.044081 -0.528591 -0.035496
9
6
0
-0.760464
0.653764 -0.013841
14
10
6
0
-2.166856
0.623657 -0.008826
11
8
0
-0.054804
1.808250 -0.02947
12
6
0
-0.636525
3.076089 -0.031153
13
6
0
-2.075804
3.063851 -0.114041
14
6
0
-2.828997
1.928934 -0.111644
15
6
0
1.510946 -0.543508 -0.057688
16
7
0
2.236541 -1.591652 -0.333352
17
6
0
3.548471 -1.157258 -0.189652
18
6
0
3.533292
0.194621
0.181605
19
8
0
2.222571
0.584208
0.267153
20
6
0
4.769597 -1.820362 -0.353114
21
6
0
5.930502 -1.082654 -0.130817
22
6
0
5.885072
0.275572
0.241131
23
6
0
4.674045
0.950773
0.406289
24
8
0
0.094225
4.037193
0.009505
25
6
0
-4.320261
2.122821 -0.268807
26
1
0
-5.841342 -2.258725
0.361702
27
1
0
-4.404010 -4.291868
0.155726
28
1
0
-1.942144 -4.010263 -0.041275
29
1
0
-4.891434 -0.052844
30
1
0
0.005587 -2.646858 -0.100591
31
1
0
-2.539289
32
1
0
4.801325 -2.866167 -0.641291
0.319500
4.040393 -0.198172
15
33
1
0
6.897629 -1.563483 -0.247391
34
1
0
6.815486
0.812206
0.402698
35
1
0
4.623709
1.996468
0.689534
36
1
0
-4.528730
3.166560 -0.516916
37
1
0
-4.732125
1.498260 -1.067377
38
1
0
-4.864510
1.893544
0.654398
-----------------------------------------------------------------
Cartesian Coordinates: Compound 6 (Gas Phase)
B3LYP optimized structure
Energy (RB3LYP) = -1049.20057333 a.u.
----------------------------------------------------------------Center Atomic
Number
Number
Atomic
Type
Coordinates (Angstroms)
X
Y
Z
----------------------------------------------------------------1
6
0
-4.077647
3.521526
0.000000
2
6
0
-2.942937
4.363651
0.000000
16
3
6
0
-1.683851
3.808737
0.000000
4
6
0
-1.510246
2.398950
0.000000
5
6
0
-2.657197
1.543969
0.000000
6
6
0
-3.939634
2.148429
0.000000
7
6
0
-0.215785
1.828341
0.000000
8
6
0
0.000000
0.461480
0.000000
9
6
0
-1.146070 -0.393487
0.000000
10
6
0
-2.446926
0.119650
0.000000
11
6
0
1.390722 -0.000114
0.000000
12
7
0
2.435798
0.780323
0.000000
13
6
0
3.520764 -0.086819
0.000000
14
6
0
3.040295 -1.404087
0.000000
15
6
0
4.899642
0.151018
0.000000
16
6
0
5.738355 -0.961438
0.000000
17
6
0
5.227235 -2.274466
0.000000
18
6
0
3.853953 -2.527187
0.000000
19
8
0
-0.917699 -1.729462
0.000000
20
6
0
-1.928765 -2.702156
0.000000
21
6
0
-3.281089 -2.176240
0.000000
22
6
0
-3.517996 -0.843337
0.000000
23
8
0
-1.592994 -3.861252
0.000000
24
1
0
-5.071909
3.959643
0.000000
25
1
0
-3.068286
5.442449
0.000000
17
26
1
0
-0.799000
4.440017
0.000000
27
1
0
-4.833022
1.533285
0.000000
28
1
0
0.653103
2.478624
0.000000
29
1
0
5.290217
1.163515
0.000000
30
1
0
6.815011 -0.816805
0.000000
31
1
0
5.918608 -3.112169
0.000000
32
1
0
3.446232 -3.532168
0.000000
33
1
0
-4.078815 -2.909842
0.000000
34
1
0
-4.544743 -0.492893
0.000000
35
8
0
1.671326 -1.343591
0.000000
-----------------------------------------------------------------
18