Access to a large stokes shift in functionalized fused coumarin derivatives by increasing the geometry relaxation upon photoexcitation: An experimental and theoretical study

Article abstract of DOI:10.1016/j.dyepig.2012.04.024

A series of new fluorophores with a fused coumarin framework were prepared. The dyes show red-shifted and enhanced absorption compared to the model compound, 7-hydroxycoumarin. The new coumarin bearing a 4- dimethylaminophenylacetylide group, shows absorption at 389 nm (ε = 14,300 M^-1 cm^-1), compared to the model compound which shows blue shifted absorption bands (ε = 11,500 M^-1 cm^-1 at 320 nm). The emission of the new coumarin bearing a 4-dimethylaminophenylacetylide group is remarkably red-shifted (λ_em = 555 nm) compared to the model compound (λ_em = 356 nm). The fluorescence quantum yields of the new coumarins are increased up to ca. 9-fold compared to the model compound. The Stokes shifts (84 nm-166 nm) are also much larger than that of the model compound. TDDFT calculations show that the fused coumarins undergo significant geometry relaxation upon photoexcitation, which is responsible for the large Stokes shift. Population of the triplet excited state was observed for the bromo-functionalized coumarin.

Full text of DOI:10.1016/j.dyepig.2012.04.024

Electronic Supplementary Information for:
Access Large Stokes Shift in Functionalized Fused Coumarin Derivatives
by Increasing the Geometry Relaxation Upon Photoexcitation: An
Experimental and Theoretical Study
Dandan Huang, Yinghui Chen and Jianzhang Zhao*
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology,
E-208 Western Campus, 2 Ling-Gong Rd., Dalian 116024, China.
E-mail: zhaojzh@dlut.edu.cn
Group Homepage http://finechem.dlut.edu.cn/photochem
S1

Synthesis of 7-hydroxy-4-methylcoumarin
O
O
OH
O
HO
O
O
OH
Resorcinol (11.0 g, 0.1 mol) was dissolved in THF (40 mL), then concentrated sulfuric acid (2 mL) was
added, ethyl acetoacetate (13.0 g, 0.1 mol) was added dropwise at room temperature. The solution was
refluxed for 3 h, then cooled to 20–25°C, ice water (100 mL) was added with constant stirring, pale yellow
solid of 7-hydroxy-4-methylcoumarin formed. The solid was collected with filtration. The crude product
1
was recrystalized from hot ethanol (10.62 g, 60.3 %). H NMR (400 MHz, CDCl3): 7.61 (d, 1H, J = 12.0
Hz), 6.83 (d, 1H, J = 8.0 Hz), 6.70 (s, 1H), 6.10 (s, 1H), 2.42 (s, 3H).
Synthesis of 8-formyl-7-hydroxy-4-methylcoumarin
HO
O
O
HO
O
O
CHO
7-Hydroxy-4-methylcoumarin (5.28 g, 0.03 mol) and hexamine (9.8 g, 0.07 mol) in glacial acetic acid (50
mL) were heated for 6–7 h, then, 20% HCl (75 mL) was added and further heated for 45 min, then cooled
to 20–25 °C and extracted with ether. Ether is evaporated and the remaining solution is poured into ice
with constant stirring, yellow solid of 8-formyl-7-hydroxy- 4-methylcoumarin formed was collected with
1
filtration. The crude product was recrystalized from hot ethanol. 613 mg, 10.0 %). H NMR (400 MHz,
CDCl3): 12.23 (s, 1H), 10.63 (s,1H,), 7.75 (d, 1H, J = 12.0 Hz ), 7.92 (d, 1H, J = 8.0 Hz), 6.21 (s, 1H,),
2.43 (s, 3H).
S2

HO
O
O
1.00
1.00
1.00
6
3.12
8
7
5
4
3
2
1
0
ppm
Fig. S1 1H NMR of C-1 (CD3OD, 400 MHz).
100
80
60
40
20
O
O
HO
C-1
0
4000
3000
2000
1000
Wavenumbers (cm-1)
Fig. S2 IR (KBr disk) spectra of C-1.
HO
O
O
CHO
1.00
1.00
1.00 1.00 1.01
3.12
10
5
0
ppm
Fig. S3 1H NMR of C-0 (CDCl3, 400 MHz).
S3

O
O
O
O
N
S
1.00
10
1.10 1.21
8
1.08
3.07
9
7
6
5
4
3
2
1
0
ppm
Fig. S4 1H NMR of C-2 (CDCl3, 400 MHz).
HDD
09:51:05
11031701 11 (0.268) AM (Cen,6, 80.00, Ar,5000.0,475.27,0.70,LS 10); Sm (SG, 2x3.00); S
384.0309
1.34e4
100
O
O
O
O
N
268.9980
244.0414
S
385.0370
515.0134
438.2116
301.1546
597.0176
679.0155
m/z
0
150 200 250 300 350 400 450 500 550 600 650
Fig. S5 TOF MS EI of C-2.
100
80
60
40
20
0
O
O
O
O
N
S
C-2
4000
3000
2000
1000
Wavenumbers (cm-1)
Fig. S6 IR (KBr disk) spectra of C-2.
S4

O
O
O
O
1.00
2.00
1.02
1.00
8.5
8.0
7.5
7.0
6.5
6.0
Br
1.00
2.00
1.00
3.00
8
7
6
5
4
3
2
1
0
ppm
Fig. S7 1H NMR of C-3 (CDCl3, 400 MHz).
1
GCT CA156
21-Jul-201108:21:05
zjz110723-1 238 (3.967) Cm (230:238-82:99)
TOF MS EI+
383.9833
3.62e4
100
O
O
O
O
%
327.9930
355.9891
384.9877
324.9873
189.0711
200
219.0827
250
137.0319
150
385.1799
400
94.5351
100
82.5343
50
426.0307
m/z
450
0
Br
300
350
Fig. S8 TOF MS EI of C-3.
O
O
O
O
Br
150
100
50
0
ppm
Fig. S9 13C NMR of C-3 (CDCl3, 100 MHz).
S5

100
80
60
40
20
0
O
O
O
O
C-3
Br
4000
3000
2000
1000
Wavenumbers (cm-1)
Fig. S10 IR (KBr) spectra of C-3.
O
O
O
O
1.00
2.01 2.05 2.02 1.14
1.99
1.00
8.5
8.0
7.5
7.0
6.5
N
1.00
2.05
1.99
6.02 3.00
3
9
8
7
6
5
4
2
1
0
ppm
Fig. S11 1H NMR of C-4 (CDCl3, 400 MHz).
2
GCT CA156
21-Jul-201109:43:43
zjz110723-2 340 (5.667) Cm (340-66:74)
TOF MS EI+
447.1472
O
O
O
1.96e3
100
O
%
448.1519
446.1432
448.4392
223.5736
250
277.0843
300
195.0759
375.1259
83.9541 173.0514
43.0188
0
m/z
50
100
150
200
350 400
450 500
N
Fig. S12 TOF MS EI of C-4.
S6

100
80
60
40
20
0
O
O
O
O
C-4
N
4000
3000
2000
1000
Wavenumbers (cm-1)
Fig. S13 IR (KBr disk) spectra of C-4.
500
400
C-1
dichloromethane
THF
toluene
300
200
100
0
methanol
ethyl acetate
acetonitrile
300
400
500
Wavelength / nm
Fig. S14 Emission spectra and excitation spectra of C-1 in different solutions (1.0×10-5 mol dm-3). λex
=300nm. 20 °C.
S7

500
400
300
200
100
0
C-2
ethyl acetate
dichloromethane
toluene
THF
acetonitrile
methanol
300 400 500 600 700
Wavelength / nm
Fig. S15 Emission spectra and excitation spectra of C-2 in different solutions (1.0×10-5 mol dm-3). λex = 380
nm. 20°C.
500
C-3
ethyl acetate
400
dichloromethane
toluene
300
THF
methanol
acetonitrile
200
100
0
300
400
500
600
Wavelength / nm
Fig. S16 Emission spectra and excitation spectra of C-3 in different solutions (1.0×10-5 mol dm-3). λex = 315
nm. 20°C.
S8

500
400
300
200
C-4
toluene
THF
ethyl acetate
100 methanol
dichloromethane
acetonitrile
0
300 400 500 600 700 800
Wavelength / nm
Fig. S17 Emission and excitation spectra of complex C-4 in different solutions (1.0×10-5 mol dm-3). λex =
390 nm. 20°C.
0.06
b
0.09
0.06
0.03
0.00
a
0.03
0.00
τ = 261 ns
828 ns
736 ns
....
184 ns
92 ns
0 ns
-0.03
-0.06
0
0
400 800 1200
Time / ns
0 . 0 2
0 . 0 0
- 0 . 0 2
4 0 0 8 0 0 1 2 0 0
T
i m
e
/ n s
300
400
500
600
Wavelength / nm
Fig. S18 Nanosecond time-resolved transient absorption difference spectra (a) and decay trace (b) of C-3
at 320 nm under are atmosphere after pulsed laser excitation (λex = 355 nm). 1.5 ×10-5 mol dm-3 in toluene,
20 °C.
S9

C2
C1
C2
C1
C2
C1
S1
S1
S1
S1
C2
C1
C2
C2
S0
C1
C1
S0
S0
S0
Fig. S19 Geometry of the coumarins at the ground state (S0) and the singlet excited state (S1). Toluene was
used as solvent in the calculation. Calculated at B3LYP/6-31g(d) level with Gaussian 09W.
Table S1: the change of C1-C2 bond length of C-1, C-2, C-3 and C-4 at optimized S0 and S1 state.
C-2
C-3
C-4
C1−C2
1.4677
1.4165
1.4820
1.4470
1.4794
1.4762
Bond length(Å)/S0
Bond length(Å)/S1
S10

Table S2. Comparison of the selected bond lengths, valence angle, torsion/dihedral angles of C-1 at
the optimized S0 and S1 geometry.
C-1
Bond lengths (Å)
S0 S1
Dihedral angle (°)
S0 S1
Valence angle (°)
S0 S1
5
3
4
H11-C8-C9-O10 0.02920 0.0046
6
7
HO
2
1
O
C5-C4-C9
C8-C9-O10
C5-C6
117.3283 116.1149
116.3657 116.4243
9 O
10
8
H
11
1.3863 1.3984
1.3922 1.3961
C8-C9
Table S3. Comparison of the selected bond lengths, valence angle, torsion/dihedral angles of C-2 at
the optimized S0 and S1 geometry.
C-2
Dihedral angle (°)
Bond angle (°)
Bond lengths (Å)
S0
S1
S0
S1
S0
S1
C11-C8-C9-O10
C11-C12-C15-C16 30.0853
C5-C4-C9
C8-C9-O10
C11-C12-C15
C12-C15-S16
C12-C15-N17
C15-N17-C18
C5-C6
C7-C8
C8-C9
C8-C11
C12-C15
0.6820
0.0280
0.0530
5
3
4
9
6
2
1
O
117.9732
116.2763
121.6382
125.2298
119.6264
88.4853
118.2728
115.4904
120.6171
131.4775
116.6050
88.2187
7
14
O
O
8
10
13
O
11
12
15
17
N
S
18
16
20
19
21
23
22
1.3564
1.4031
1.4134
1.4310
1.4677
1.2967
1.4180
1.3642
1.4245
1.4299
1.3963
1.4165
1.2700
1.4477
C15-S16
C18-C19
S11

Table S4. Comparison of the selected bond lengths, valence angle, torsion/dihedral angles of C-3 at
the optimized S0 and S1 geometry.
Dihedral angle (°)
Bond angle (°)
Bond lengths (Å)
C-3
S0
S1
S0
S1
S0
S1
C11-C8-C9-O10
C11-C12-C15-C16 35.3380 0.0169
C5-C4-C9
C8-C9-O10
C11-C12-C15
C12-C15-C16
C12-C15-C17
C15-C17-C18
C2-C3
C5-C6
C7-C8
C8-C11
C9-O10
0.4191
0.4146
5
3
4
6
7
2
1
O
118.0245
116.2444
121.8266
121.9545
119.8240
121.3555
118.1738
115.5494
120.0370
123.0607
120.5177
122.0049
14
13
O
O
O
9
8
10
11
12
15
17
18
20
16
19
Br
21
1.3591
1.3834
1.4017
1.4338
1.3579
1.4820
1.4063
1.9131
1.3640
1.3997
1.4301
1.3888
1.3477
1.4470
1.4333
1.8871
C12-C15
C15-C16
C20-Br21
Table S5. Comparison of the selected bond lengths, valence angle, torsion/dihedral angles of C-4 at
the optimized S0 and S1 geometry.
Dihedral angle (°) Bond angle (°)
Bond lengths (Å)
C-4
S0
S1
S0
S1
S0
S1
C11-C8-C9-O10
0.3048
0.3134
C11-C12-C15-C16 33.8229 22.8835
C5-C4-C9
C8-C9-O10
C11-C12-C15
C12-C15-C16
C12-C15-C17
C5-C6
118.0512 118.4782
116.2325 115.6279
121.8887 120.1355
122.2114 122.5926
119.8661 120.3326
5
3
4
6
2
1
7
14
13
O
O
9 O
10
O
8
11
12
15
1.3833
1.4017
1.4129
1.4794
1.4083
1.4085
1.4212
1.2190
1.4203
1.3958
1.4203
1.4242
1.4762
1.4168
1.4178
1.4142
1.2255
1.4017
16
19
17
18
C7-C8
C8-C9
20
21
23
C12-C15
C15-C16
C15-C17
C20-C21
C21-C22
C22-C23
22
28
24
25
27
26
N
29
30
S12

Table S6. Selected electronic excitation energies (eV), corresponding oscillator strengths (f), main configurations and
CI coefficients of the low-lying electronically excited states of C-4. The excitation energy was calculated with MPW1K XC
functional, based on the optimized ground state geometry (B3LYP/6-31G(d). Calculated with Gaussian 09W.
Electronic
TDDFT// MPW1K XC /6-31G(d)
Transition a
Energy b
f c
Composition d
H-1→L
H→L
CI e
3.16 eV (392 nm)
0.9883
0.1716
0.6560
0.1475
0.1056
0.1619
0.1634
0.6603
0.2120
0.5699
0.1912
0.2616
S0→S1
H→L+1
H→L+2
H-1→L+1
H→L
H→L+1
H−5→L
H−1→L
H→L
3.75 eV (331 nm)
3.46 eV (358 nm)
0.0500
1.1128
S0→S2
S0→S3
H→L+2
a Only low-lying states are selected. b Only the low-lying excited state and some major allowed transitions were presented c
d
Oscillator strength. Only the main configuration interaction (CI) coefficients >0.1 are presented. H stands for HOMO
and L stands for LUMO. e CI coefficients are in absolute values.
S13

10°
0°
S1
T1
Fig. S16 Geometry of the coumarin C-3 at the ground state (S1) and the triplet excited state (T1). Toluene was used as
solvent in the calculation. Calculated at B3LYP/6-31g(d) level with Gaussian 09W.
Table S7. Comparison of the selected bond lengths, valence angle, torsion/dihedral angles of C-3 at the
optimized T1 and S1 geometry.
dihedral angle (°)
valence angle (°)
S1
bond lengths (Å)
T1 S1
C-3
T1
0.0001
S1
T1
5
3
C11-C8-C9-O10
0.4146
10.8705
4
6
7
2
C11-C12-C15-C16 0.0169
C5-C4-C9
C8-C9-O10
C11-C12-C15
C12-C15-C16
C12-C15-C17
C15-C17-C18
C2-C3
1
14
13
O
O
O
9
11
O
118.3192
115.2310
120.7734
123.6282
120.4080
122.1080
118.1738
115.5494
120.0370
123.0607
120.5177
122.0049
8
10
12
15
17
18
16
19
20
Br
21
1.3600
1.3997
1.4247
1.3882
1.3591
1.4244
1.4400
1.8975
1.3640
1.3997
1.4301
1.3888
1.3477
1.4470
1.4333
1.8871
C5-C6
C7-C8
C8-C11
C9-O10
C12-C15
C15-C16
C20-Br21
S14

Table S8. Selected electronic excitation energies (eV) and corresponding oscillator strengths (f). Main configurations
and CI coefficients of the low-lying electronically excited states of C-3.
Electronic
transition
TDDFT//B3LYP/6-31G(d)
Energy (eV)
f c
Composition d
CI e
3.49 eV (355 nm ) 0.6657
0.6856
0.1494
0.1511
0.3586
0.5681
0.1014
0.6957
0.1051
0.5092
0.3176
0.1441
0.1900
0.1403
0.6301
0.1215
S0→S1(EX)
H→L
H−1 →L
H→L
3.66 eV (338 nm) 0.0712
S0→S2(EX)
H→L+1
H−1→L
H−3→L
H→L
H−7→L
H−1→L
H−1→L+1
H→L+1
H−2→L
H−1→L+1
H→L
1.42 eV (873 nm ) 0.0000
2.79 eV (444 nm) 0.0000
S0→T1(EM)
S0→T2 (EM)
2.39 eV (519 nm) 0.0000
S0→T1 (EX)
H→L+1
a Only low-lying states are selected. b Only the low-lying excited state and some major allowed transitions were presented c
d
Oscillator strength. Only the main configuration interaction (CI) coefficients >0.1 are presented. H stands for HOMO
and L stands for LUMO. e CI coefficients are in absolute values.
S15

Table S9. Selected electronic excitation energies (eV) and corresponding oscillator strengths (f). Main
configurations and CI coefficients of the low-lying electronically excited states of C-4. a Dichloromethane was
used as solvent in the calculations.
Electronic
transition
TDDFT//B3LYP/6-31G(d)
Energy
f
Composition
L→H
CI
2.00 eV (618 nm)
2.74 eV (452 nm)
3.09 eV (401nm)
0.9692
0.0012
0.8577
0.7044
0.7020
0.2348
0.6601
S1→S0
S2→S0
S3→S0
L+1→H
L+2→H
L→H−1
a Excitations were calculated by TDDFT//B3LYP/6-31G(d), based on the optimized ground state geometries. The
emissions were calculated based on the optimized excited state geometries. Dichloromethane was used as solvent in the
calculations. b Only the low-lying excited state and some major allowed transitions were presented c Oscillator strength. d
Only the main configuration interaction (CI) coefficients >0.1 are presented. H stands for HOMO and L stands for
LUMO. e CI coefficients are in absolute values.
Table S10. Selected electronic excitation energies (eV) and corresponding oscillator strengths (f).
a
Main configurations and CI coefficients of the low-lying electronically excited states of C-4. Acetonitrile
was used as solvent in the calculations.
Electronic
transition
TDDFT//B3LYP/6-31G(d)
Energy
f
Composition
L→H
CI
1.98 eV (625 nm)
2.76 eV (450 nm)
3.07 eV (403nm)
1.0340
0.0013
0.8655
0.7039
0.7018
0.2361
0.6590
S1→S0
S2→S0
S3→S0
L+1→H
L+2→H
L→H−1
a Excitationswere calculated by TDDFT//B3LYP/6-31G(d), based on the optimized ground state geometries. The
emissions were calculated based on the optimized excited state geometries. Acetonitrile was used as solvent in the
calculations. b Only the low-lying excited state and some major allowed transitions were presented c Oscillator strength. d
Only the main configuration interaction (CI) coefficients >0.1 are presented. H stands for HOMO and L stands for
LUMO. e CI coefficients are in absolute values.
S16

C-1 (DFT//B3LYP/ rb3lyp/6-31g(d))
Ground state geometry (S0 state)
Symbolic Z-matrix:
O
O
HO
Charge = 0 Multiplicity = 1
C
C
C
C
C
C
H
C
H
H
C
C
H
O
O
O
H
C
H
H
H
-2.56264720
-1.47085011
-0.18448401
0.04911200
-1.07695408
-2.36563018
-1.61637012
1.42468611
-0.93723007
-3.22175525
2.42263418
2.18293617
3.46739327
0.84105306
3.02355523
-3.80335129
-4.47188534
1.72818113
1.30058510
1.30078010
2.80653621
-0.33723403
-0.00006800
-0.00051400
-0.00023900
-0.00001000
0.00003000
-0.00006000
-0.00129900
0.00002200
-0.00000500
0.00031300
-0.00001000
0.00004900
-0.00001900
-0.00038000
0.00054100
0.00045400
0.00104200
-0.00002200
-0.88248207
0.88258507
-0.00012100
-1.20351109
-0.67111705
0.72234905
1.56612412
1.05511508
-2.27740018
1.18542609
2.64229120
1.72609013
0.26421702
-1.16964509
0.55480104
-1.56735412
-2.03743115
-0.89799507
-0.19519201
2.66014120
3.15170724
3.15163824
2.83712122
C-1 (TDDFT//B3LYP/ rb3lyp/6-31g(d))
Excited states geometry (S1 state)
Symbolic Z-matrix:
Charge = 0 Multiplicity = 1
C
C
C
C
C
C
H
C
H
H
-2.57201580
-1.48370481
-0.18796525
0.07444570
-1.06401539
-2.35939610
-1.62958997
1.42520070
-0.93252187
-3.21401298
-0.34083400
-1.21160711
-0.69192806
0.74917463
1.58958965
1.06281318
-2.28616587
1.21305683
2.66578900
1.73674104
0.00013085
-0.00001274
-0.00014107
-0.00001904
0.00014405
0.00019744
-0.00009487
-0.00003683
0.00021285
0.00029699
S17

C
C
H
O
O
O
H
C
H
H
H
2.45318382
2.21330585
3.49738997
0.81189794
2.99543182
-3.82205811
-4.49765650
1.73824655
1.32521726
1.32533418
2.81995510
0.23998264
-1.15483454
0.53340133
-1.58344890
-2.09114582
-0.88585701
-0.18894925
2.67778283
3.19076538
3.19063021
2.84222577
0.00006286
-0.00004273
0.00016656
-0.00045219
-0.00010942
0.00017230
0.00022708
0.00005889
-0.88329025
0.88354572
0.00000030
C-2 (DFT//B3LYP/ rb3lyp/6-31g(d))
Ground state geometry (S0 state)
Symbolic Z-matrix:
O
O
O
O
Charge = 0 Multiplicity = 1
N
S
C
C
C
C
C
C
C
H
H
C
H
O
C
O
C
H
H
H
C
C
O
O
C
H
C
1.80638628
1.62194220
2.77542227
4.06636286
4.18870025
3.08092037
5.19598666
5.17751228
3.17480901
4.95163484
5.75775846
3.31656681
3.61634026
2.56304339
6.60197562
6.80116434
6.77109331
7.32826118
-0.79716698
-0.59606036
0.73638062
-1.43817291
0.28307926
0.14391020
-2.17019288
1.94935724
0.56016084
-0.25386513
0.29499129
1.70235322
2.52864768
-0.61853356
2.14741091
3.60711431
-1.95380638
-2.67683735
-3.68708719
-2.51666244
-1.59174324
-0.08474195
0.49629891
0.58204976
-0.89899796
0.88709345
2.34588869
2.78026949
3.19935309
0.05508779
-1.01798748
0.36879102
-0.08865716
-0.01882705
0.04827350
0.04357377
-0.02791366
-0.09252979
0.11319238
-0.03226216
-0.14728229
0.18016663
0.23375709
0.24419338
0.18586884
0.11663050
0.11106630
-0.79741040
0.96516209
0.16337442
-0.06555840
-0.17095232
-0.15641796
-0.28326187
-0.00391409
0.07894641
-0.04701680
S18

C
C
C
C
C
H
C
H
H
H
S
-4.34703452
-4.18880199
-5.61496882
-5.27034356
-6.68963430
-5.73066882
-6.51900957
-5.14483913
-7.67577564
-7.37440258
-2.51547037
-3.19672390
0.22852185
-1.04090213
0.62704488
-1.90970290
-0.23689864
1.59904039
-1.49335618
-2.88034286
0.05954063
-2.15210892
-1.25139733
0.98771820
0.34348758
-0.26814759
0.79639252
-0.43455942
0.63098506
1.26519690
0.02073639
-0.90381229
0.97613784
-0.09831744
-0.73367215
0.44744450
N
C-2 (TDDFT//B3LYP/ rb3lyp/6-31g(d))
Excited states geometry (S1 state)
Symbolic Z-matrix:
Charge = 0 Multiplicity = 1
C
C
C
C
C
C
C
H
H
C
H
O
C
O
C
H
H
H
C
C
O
O
C
H
C
C
1.80915589
1.58371591
2.74749224
4.04458859
4.19851646
3.09034835
5.15238865
5.19343160
3.20504586
4.88481672
5.67921824
3.21470928
3.54103700
2.51105726
6.56879843
6.76305289
6.76266590
7.28115070
-0.83016168
-0.59651201
0.75549955
-1.40906386
0.27267040
0.11661033
-2.16177266
-4.37982032
1.98906078
0.58253279
-0.24826996
0.27672760
1.68512839
2.52966744
-0.66403216
2.11472495
3.60821288
-1.99839394
-2.73649366
-3.70189536
-2.53374579
-1.58477962
-0.15824956
0.46415840
0.46455613
-0.98660378
1.00960906
2.44346005
2.85553585
3.34152254
0.10208756
-0.96909903
0.52673281
0.29808482
-0.00082953
-0.00043370
-0.00013754
0.00005050
-0.00010020
-0.00050593
0.00037718
0.00008157
-0.00064421
0.00047915
0.00073885
0.00035928
0.00021843
0.00003236
0.00059217
-0.88131053
0.88229459
0.00093364
0.00037535
0.00004801
-0.00168987
0.00082263
0.00001292
0.00086233
0.00065871
0.00052294
S19

C
C
C
C
H
C
H
H
H
S
-4.07557039
-5.71445589
-5.09765877
-6.71633426
-5.95599974
-6.41335160
-4.85230257
-7.75639478
-7.22042951
-2.38354386
-3.30061587
-1.11731223
0.69839817
-2.08945763
-0.27664102
1.75538971
-1.66070321
-3.14606258
0.03482476
-2.38567488
-1.36880961
1.14740709
-0.00035730
0.00101980
-0.00074147
0.00061586
0.00175248
-0.00024688
-0.00145251
0.00097024
-0.00057669
-0.00104921
0.00103312
N
C-3 (DFT//B3LYP/ rb3lyp/6-31g(d))
Ground state geometry (S0 state)
Symbolic Z-matrix:
O
O
O
Charge = 0 Multiplicity = 1
O
C
C
C
C
C
C
C
H
H
C
H
O
C
O
C
H
H
H
C
C
O
O
C
H
C
-2.30876552
-2.03107288
-3.12964318
-4.45426810
-4.67020169
-3.61789196
-5.52145478
-5.68617501
-3.78091139
-5.19035513
-5.94756026
-3.44567630
-3.82056384
-2.83083947
-6.95957064
-7.18614036
-7.18173830
-7.63151541
0.36731706
0.05705213
-1.29258406
0.84974276
-0.65893851
-0.45095081
1.78470653
1.91385369
0.54127196
-0.34595207
0.11600565
1.51241676
2.40948971
-0.87115968
1.89081953
3.48010730
-2.18794385
-2.96305006
-3.81032357
-2.66084696
-1.66923691
-0.43116408
0.13860393
0.22058649
-1.29140359
1.02395990
2.46307742
2.81508601
3.37712055
0.12607217
-0.93568573
0.59121322
0.08019632
0.01888253
-0.02305558
-0.00266129
0.06160157
0.10280244
-0.05013698
0.07839363
0.15070659
-0.11012018
-0.14731166
-0.17896306
-0.12808036
-0.08276273
-0.03310994
0.87613650
-0.88664885
-0.07490779
0.03783080
0.09395532
0.11569259
0.12676035
-0.00666062
-0.08102583
0.04236825
Br
S20

C
C
C
H
C
H
C
H
H
Br
2.78421924
2.15368175
4.10065212
2.53247704
3.46714329
1.41138512
4.43089872
4.86066341
3.73740418
6.23943570
1.30890658
-0.58815751
0.85383217
2.22761436
-1.05152601
-1.14366458
-0.32454784
1.41130975
-1.95878274
-0.94772659
-0.63854097
0.71332726
-0.66615817
-1.15298888
0.69551544
1.27868089
0.00011044
-1.20236848
1.22433247
-0.02963466
C-3 (TDDFT//B3LYP/ rb3lyp/6-31g(d))
Excited states geometry (S1 state)
Symbolic Z-matrix:
Charge = 0 Multiplicity = 1
C
C
C
C
C
C
C
H
H
C
H
O
C
O
C
H
H
H
C
C
O
O
C
H
C
C
C
-2.30418371
-2.00381764
-3.12779072
-4.45117011
-4.67440201
-3.60774747
-5.50528202
-5.68952375
-3.78390073
-5.16933889
-5.92669327
-3.40271830
-3.80516818
-2.82315604
-6.94458079
-7.16827650
-7.17030685
-7.61576572
0.39758861
0.07597112
-1.28896621
0.83621428
-0.67776406
-0.47822849
1.76965142
2.88582878
2.07481024
1.94656125
0.54854867
-0.34893953
0.10950465
1.50884253
2.41503233
-0.88902356
1.88816676
3.48523263
-2.21073972
-2.98664326
-3.81967615
-2.67592767
-1.66152886
-0.45538295
0.14047532
0.17473557
-1.31731110
1.08541192
2.49852047
2.85888380
3.45298263
0.13595683
-0.92453233
0.62580137
1.49644329
-0.76075128
0.02837337
0.00721650
-0.01174490
-0.00113209
0.02625957
0.03989609
-0.01888950
0.03431806
0.05621234
-0.04391046
-0.05731234
-0.07458697
-0.05376350
-0.03681529
-0.00885750
0.88478269
-0.87813817
-0.02484885
0.02069987
0.03009241
0.03029858
0.05025872
0.00933741
-0.04295453
0.02026184
-0.20437603
0.24215206
S21

C
H
C
H
C
H
H
Br
4.18164428
2.69691271
3.37210485
1.28284281
4.43053281
5.00930982
3.57313944
6.20566234
1.02407637
2.54679069
-1.23421595
-1.46736123
-0.34430263
1.70117690
-2.28458504
-0.98439813
-0.21275787
-0.37260230
0.23934733
0.45283838
0.00733064
-0.39385113
0.41894469
-0.01496687
C-3 (DFT//B3LYP/ rb3lyp/6-31g(d))
Triplet state geometry
Symbolic Z-matrix:
Charge = 0 Multiplicity = 3
C
C
C
C
C
C
C
H
H
C
H
O
C
O
C
H
H
H
C
C
O
O
C
H
C
C
C
C
H
C
H
2.30023200
2.00681600
3.14368800
4.45875300
4.67206300
3.59563100
5.53002700
5.68326900
3.75612000
5.20725800
5.96968100
3.46910900
3.84084400
2.85006300
6.96554600
7.18526900
7.18468100
7.64350400
-0.42118300
-0.07479200
1.27755100
-0.83375700
0.69278300
0.50249900
-1.77614700
-2.90460300
-2.08242400
-4.20099500
-2.72688800
-3.38246700
-1.29092700
1.92771000
0.53091800
-0.34901100
0.12131700
1.52285800
2.41506900
-0.86293100
1.91179500
3.48762000
-2.18383900
-2.95483300
-3.81670600
-2.66370100
-1.67378400
-0.41434800
0.19945900
0.19914700
-1.27095000
1.06536500
2.48805400
2.83822300
3.43978400
0.09784000
-0.96330800
0.62062000
1.51129700
-0.78413700
1.04094700
2.57613000
-1.25278000
-1.52064000
-0.00030700
-0.00043700
-0.00017100
0.00028800
0.00047400
0.00017500
0.00056500
0.00083300
0.00026400
0.00035500
0.00055000
-0.00035900
-0.00014100
-0.00038300
0.00110200
-0.88074500
0.88331500
0.00117900
-0.00046500
-0.00040400
-0.00082600
-0.00020800
-0.00071500
-0.00074000
-0.00033800
0.00064600
-0.00127300
0.00088700
0.00125900
-0.00110100
-0.00231800
S22

C
-4.44580000
-5.03239700
-3.57807100
-6.23291000
-0.34221200
1.73747800
-2.31944000
-0.98048000
0.00003800
0.00172300
-0.00185800
0.00044800
H
H
Br
C-4 (DFT//B3LYP/ rb3lyp/6-31g(d))
Ground state geometry (S0 state)
Symbolic Z-matrix:
O
O
O
Charge = 0 Multiplicity = 1
O
C
C
-5.07986318
-4.57914907
-5.51775816
-6.90056954
-7.34393721
-6.45278774
-7.79065314
-8.40831406
-6.78914169
-7.24770913
-7.86691493
-5.26112292
-5.81889770
-5.00582762
-9.28173180
-9.59870066
-9.60883742
-9.80271622
-2.29026895
-2.83568843
-4.22599959
-2.20852762
-3.15741972
-2.77710580
-0.82384880
0.06004934
-0.27414730
1.42825823
-0.33062533
1.09285709
-0.92593098
1.97597303
2.09140239
-1.72026868
-0.41625130
0.63568636
0.39862926
-0.93912584
-1.99329134
1.54445213
-1.14475962
-3.01978938
2.78514204
3.67180396
4.09520956
3.02532181
1.88890639
1.34842267
0.86195710
0.70747573
2.30519906
-1.28444473
-2.64929263
-2.77330296
-3.68080155
-0.23377116
0.77495996
-1.08898337
-2.00123500
0.05887889
-1.76499558
-2.89860836
0.29848403
0.76241493
-0.61015199
-2.47591775
-0.13944623
-0.02327363
0.06977963
0.04332868
-0.07805760
-0.16826932
0.14192247
-0.10061285
-0.25973906
0.25641557
0.33350336
0.38249949
0.28388744
0.18403640
0.11645949
-0.81383311
0.94401233
0.19740207
-0.09477742
-0.20858457
-0.22494778
-0.29540632
0.00250126
0.11925919
-0.10677211
0.50127536
-0.71020227
0.52152005
0.96415055
-0.69679121
-1.22015497
-0.07593557
1.00452886
C
C
C
C
C
H
H
C
H
O
C
O
C
H
H
H
C
C
O
O
C
H
C
C
C
C
H
C
H
C
H
N
S23

H
C
C
C
C
C
C
H
C
H
C
H
H
N
C
H
H
H
C
H
H
H
1.49338651
3.37714330
4.57915099
5.98007408
6.86993547
6.53628419
8.23766318
6.47229412
7.90237494
5.87711301
8.79921692
8.87556461
8.27627772
10.16058556
10.69532791
10.32712193
11.78326780
10.43601719
11.04307419
10.96564974
12.07511615
10.82508127
1.18554239
-0.37294677
-0.17057732
0.06276518
-0.86952099
1.23722610
-0.64674873
-1.78196680
1.47057355
1.97713868
0.53073783
-1.39391022
2.39171138
0.75059714
2.01769138
2.87170020
1.99663770
2.19262956
-0.18316121
-1.19043584
0.15004412
-0.25356585
-1.17742243
-0.06023365
-0.04530846
-0.02600414
0.54719829
-0.57427445
0.57123948
0.98192022
-0.55449875
-1.01889896
0.01467296
1.02762130
-0.98472757
0.02286247
-0.45115441
0.13641616
-0.37573678
-1.50307913
0.70506599
0.27658910
0.58815915
1.78105370
C-4 (TDDFT//B3LYP/ rb3lyp/6-31g(d))
Excited states geometry (S1 state)
Symbolic Z-matrix:
Charge = 0 Multiplicity = 1
C
C
C
C
C
C
C
H
H
C
H
O
C
O
C
H
-5.07793030
-4.55660247
-5.51596462
-6.89855041
-7.35506348
-6.44410342
-7.77497986
-8.41836599
-6.78029914
-7.23027078
-7.85018029
-5.24085564
-5.80372645
-5.00382681
-9.26754017
-9.58470551
-1.73001184
-0.41219828
0.63761010
0.40302420
-0.93380689
-1.98894446
1.55746958
-1.14102348
-3.01811878
2.80222147
3.68998097
4.11153989
3.03531281
1.90009655
1.36894105
0.86619661
-0.11743874
-0.02276422
0.05327341
0.03020548
-0.06976978
-0.14083039
0.10978843
-0.08936294
-0.21290271
0.20412065
0.26585759
0.30963371
0.22816288
0.14824288
0.08702438
-0.83479486
S24

H
H
C
C
O
O
C
H
C
C
C
C
H
C
H
C
H
H
C
C
C
C
C
C
H
C
H
C
H
H
N
C
H
H
H
C
H
H
H
-9.59596736
-9.78714460
-2.28030417
-2.80982792
-4.22443505
-2.21369544
-3.16280083
-2.77737502
-0.82056983
0.10135318
-0.28480455
1.46539159
-0.27658463
1.07769575
-0.94957442
1.98487704
2.14974629
1.45688195
3.37767228
4.58522200
5.96674500
6.87687590
6.50521233
8.23310755
6.48553466
7.85995313
5.82760917
8.77392823
8.88921045
8.22661507
10.11552914
10.65767075
10.26751064
11.74158044
10.40753967
11.04282363
10.95986975
12.06118312
10.84778128
0.73904888
2.32816259
-1.33440324
-2.66531762
-2.79597727
-3.73491135
-0.23398243
0.77113898
-1.11465962
-2.10633043
0.13060533
-1.86551925
-3.07244925
0.38094817
0.90618152
-0.61444380
-2.64200913
1.34456684
-0.36997053
-0.16148973
0.07508499
-0.92470679
1.32237498
-0.69773417
-1.88205647
1.55858263
2.09729625
0.55474915
-1.48574838
2.52150474
0.78433166
2.07401068
2.88900546
2.05394897
2.27571713
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S25