Supporting Information
C3h-symmetric and Cs-symmetric Triformyl Triindolo-Truxenes:
Synthesis and Properties
Jun-Bo Chen,[a] Ru-Qiang Lu,[a] Xin-Chang Wang,[b] Hang Qu,[a] Hao-Liang Liu,[a] Hui
Zhang,[a] and Xiao-Yu Cao*[a]
[a]
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center
of Chemistry for Energy Materials (iChEM), Key Laboratory of Chemical Biology of Fujian
Province, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen
University, Xiamen 361005, P. R. China.
E-mail: xcao@xmu.edu.cn
[b]
Department of Electronic Science and Engineering, Xiamen University, Xiamen 361005, P. R.
China.
Table of Contents
1. General remarks…………….…...…………………………...……..………..…..S1
2. Synthetic procedures and characterization……………………............……….S2
3. The isosurfaces of the Fukui function f -………………………………………..S7
4. UV/Vis absorption and fluorescence……...………………………………….…S8
5. X-ray crystallographic analysis……..…………..………………………….….S11
6. Concentration-dependent 1H NMR experiments and the determination of
association constants……………………………………………………….…...…S13
7. 1D and 2D NMR spectra………………………………..…..……….....………S16
8. Reference……………………………………………….………………………..S32
1. General remarks
All chemicals and solvents from commercial sources were used without further purification unless
otherwise mentioned. 1H and 13C NMR spectra were recorded with a Bruker Avance II 400 MHz,
Avance III 500 MHz, Ascend 600 MHz, or Avance III HD 850MHz NMR spectrometer.
High-resolution mass spectra were recorded with a Bruker En Apex Ultra 7.0 T FTMS mass
spectrometer. Absorption spectra were recorded with a SHIMADZU UV-2700 spectrometer.
Fluorescence
measurements
were
performed
with
a
HITACHI
F-7000
fluorescence
spectrophotometer. Cyclic voltammetry was performed with a CHI660E electrochemical
workstation in anhydrous dichloromethane containing n-Bu4NPF6 (0.1 M) as supporting
electrolyte. All potentials were recorded versus Ag/AgCl (saturated) as a reference electrode. The
scan rate was 100 mV s-1. Single crystal X-ray diffraction data were collected with a Rigaku
SuperNova diffractometer by using CuKa (λ = 1.54184 Å) microfocus X-ray sources.
Computational
methods:
the
optimizations
of
structures
were
performed
at
the
B3LYP/6-311G(d, p) level of theory in the gas phase on Gaussian 09, Revision E.01.[1] Harmonic
vibrational frequency calculations were performed for all of the stationary points to confirm them
as local minima. Single-point energies of neutral 1a and 2a and cationic 1a+ and 2a+ for Fukui
function analysis were calculated at B3LYP/6-311G(d, p) level of theory in the gas phase using the
optimized structures. The optimized structures were further used in time-dependent density
functional theory (TD-DFT) calculations. The TD-DFT calculations were performed at the
B3LYP/6-31+G(d) level of theory in the gas phase.
S1
2. Synthetic procedures and characterization
Synthesis of 1b and 1c: Compound 1a was obtained according to the known procedure.[2]
Compound 1a (1.46 g, 1.55 mmol) was dissolved in anhydrous dichloromethane (80 mL).
1,1-dichlorodimethyl ether (1.14 g, 9.92 mmol) and titanium tetrachloride (3.6 g, 18.9 mmol) were
added to the solution. The reaction mixture was stirred at room temperature overnight under a
nitrogen atmosphere then quenched with water. The crude products were extracted with
dichloromethane (15 mL) for three times. The organic phase was combined and washed with brine
then dried over anhydrous sodium sulphate. The crude products were purified by column
chromatography on silica gel with petroleum ether/dichloromethane (2:1, v/v) as mobile phase to
give 1b (0.52 g, 33%) and 1c (0.45 g, 28%) as yellow solids. 1H NMR for 1b (400 MHz, C6D6,
343 K), δ (ppm) 10.07 (s, 3H), 8.13 (s, 3H), 7.94 (s, 3H), 7.70 (s, 3H), 7.51–7.44 (m, 6H), 3.71 (s,
6H), 2.33–2.29 (m, 12H), 1.36–1.30 (m, 12H), 1.18–1.08 (m, 12H), 0.87–0.84 (m, 18H).
13
C
NMR for 1b (101 MHz, C6D6, 343 K), δ (ppm) 190.74, 152.10, 151.62, 147.21, 145.92, 141.88,
139.90, 136.89, 136.85, 135.83, 130.90, 123.27, 120.09, 120.05, 114.56, 55.66, 40.93, 36.77,
27.14, 23.65, 14.03. ESI-HRMS for 1b (m/z): [M+Na]+ calcd. for C75H78O3Na+, 1049.5843; found,
1049.5863. 1H NMR for 1c (400 MHz, C6D6, 343 K), δ (ppm) 10.11 (s, 2H), 9.82 (s, 1H), 9.24 (s,
1H), 8.13 (d, J = 4.7 Hz, 2H), 7.86 (s, 1H), 7.85 (s, 1H), 7.75 (m, 1H), 7.74 (s, 1H), 7.70 (s, 1H),
7.54 (d, J = 7.8 Hz, 1H), 7.52 (d, J = 7.2 Hz, 1H), 7.44–7.38 (m, 4H), 7.35 (t, J = 7.4 Hz, 1H),
3.74 (s, 2H), 3.58 (s, 4H), 2.40–2.34 (m, 12H), 1.39–1.32 (m, 12H), 1.23–1.11 (m, 12H), 0.92–
0.88 (m, 18H). 13C NMR for 1c (101 MHz, C6D6, 343 K), δ (ppm) 190.91, 190.46, 153.50, 152.25,
151.63, 151.49, 151.06, 147.77, 147.57, 146.79, 146.22, 145.67, 142.41, 142.14, 142.03, 142.00,
140.33, 139.72, 139.51, 137.32, 136.85, 136.71, 136.62, 136.44, 135.70, 133.47, 133.15, 130.77,
126.96, 123.82, 123.57, 120.69, 120.41, 120.15, 119.99, 119.28, 114.71, 114.30, 55.86, 55.70,
54.91, 41.56, 41.22, 41.10, 36.75, 27.19, 26.89, 23.86, 14.12. Some signals of 1c overlapped each
S2
other that were hardly recognized. ESI-HRMS for 1c (m/z): [M+Na]+ calcd. for C75H78O3Na+,
1049.5843; found, 1049.5859.
Synthesis of 2b and 2c: Compound 2a was obtained according to the known procedure.[2]
Compound 2a (6.1 g, 6.47 mmol) was dissolved in 60 mL anhydrous dichloromethane.
1,1-dichlorodimethyl ether (2.77 g, 24.1 mmol) and titanium tetrachloride (9.2 g, 48.5 mmol) were
added to the solution. The reaction was stirred at room temperature overnight under a nitrogen
atmosphere then quenched with water. The crude products were extracted by dichloromethane,
washed with brine, and dried over anhydrous sodium sulphate. The crude products were purified
by column chromatography on silica gel with petroleum ether/dichloromethane (2:1, v/v) as
mobile phase to give 2b (2.3 g, 35%) and 2c (1.9 g, 29%) as pale yellow solids. 1H NMR for 2b
(850 MHz, CDCl3, 298 K), δ (ppm) 10.12 (s, 3H), 8.92 (s, 3H), 8.14 (s, 3H), 8.10 (d, J = 7.6 Hz,
3H), 8.03 (d, J = 7.5 Hz, 3H), 7.75 (s, 3H), 4.15 (s, 6H), 3.17–3.13 (m, 6H), 2.32–2.29 (m, 6H),
0.98–0.91 (m, 12H), 0.68–0.60 (m, 12H), 0.46 (t, J = 7.4 Hz, 18H). 13C NMR for 2b (214 MHz,
CDCl3, 298 K), δ (ppm) 192.18, 155.49, 148.63, 145.27, 144.06, 143.85, 139.54, 139.00, 138.28,
134.88, 129.94, 126.04, 119.55, 119.23, 116.86, 55.52, 36.90, 36.69, 26.74, 22.90, 13.84.
ESI-HRMS for 2b (m/z): [M+Na]+ calcd. for C75H78O3Na+, 1049.5843; found, 1049.5843. 1H
NMR for 2c (850 MHz, CDCl3, 298 K), δ (ppm) 10.71 (s, 1H), 10.12 (s, 1H), 10.11 (s, 1H), 9.88
(s, 1H), 8.93 (s, 1H), 8.92 (s, 1H), 8.14 (s, 1H), 8.13 (s, 1H), 8.10 (d, J = 3.9 Hz, 1H), 8.09 (d, J =
3.9 Hz, 1H), 8.03 (d, J = 4.2 Hz, 2H), 8.02 (d, J = 4.5 Hz, 1H), 7.98 (d, J = 7.3 Hz, 1H), 7.85 (d, J
= 7.0 Hz, 1H), 7.79 (s, 1H), 7.75 (s, 1H), 7.74 (s, 1H), 7.52 (t, J = 7.2 Hz, 1H), 4.15–4.14 (m, 6H),
3.45–3.42 (m, 2H), 3.18–3.14 (m, 4H), 2.36–2.33 (m, 2H), 2.32–2.28 (m, 4H), 0.98–0.90 (m,
12H), 0.68–0.60 (m, 12H), 0.46–0.44 (m, 12H), 0.41 (t, J = 7.4 Hz, 6H).
13
C NMR for 2c (214
MHz, CDCl3, 298 K), δ (ppm) 192.57, 192.23, 192.20, 156.01, 155.61, 154.99, 148.82, 148.73,
145.76, 145.73, 145.13, 144.95, 144.12, 144.08, 143.78, 143.70, 143.57, 142.95, 139.75, 139.68,
S3
139.63, 139.25, 138.91, 138.90, 138.75, 138.37, 138.06, 134.83, 134.78, 132.78, 132.30, 130.35,
129.90, 129.85, 126.09, 126.08, 126.01, 122.25, 119.54, 119.49, 119.44, 119.21, 118.53, 116.85,
116.71, 56.01, 55.49, 55.20, 37.07, 36.92, 36.90, 36.69, 36.41, 26.76, 22.93, 22.92, 22.90, 13.85.
Some signals of 2c overlapped each other that were hardly recognized. ESI-HRMS for 2c (m/z):
[M+Na]+ calcd. for C75H78O3Na+, 1049.5843; found, 1049.5828.
Synthesis of 4: Compound 3 was obtained according to the known procedure.[3] Compound 3 (3.0
g, 4.4 mmol) and 2-iodo-5-methylbenzoyl chloride (5.9 g, 21.0 mmol) were dissolved in
dichloromethane (30 mL). Anhydrous aluminum chloride (2.5 g, 18.7 mmol) was added to the
solution slowly. The resulting black reaction was stirred at room temperature overnight under a
nitrogen atmosphere then quenched with water. The crude product was extracted by
dichloromethane (15 mL) for three times. The organic phase was combined and washed with brine,
then dried over anhydrous sodium sulphate. The crude product was purified by column
chromatography on silica gel with petroleum ether/dichloromethane (1:1, v/v) as mobile phase to
give 4 (5.2 g, 84%) as a pale yellow solid. 1H NMR (500 MHz, CDCl3, 298 K), δ (ppm) 8.44 (d, J
= 8.4 Hz, 3H), 7.99 (s, 3H), 7.83 (d, J = 8.2 Hz, 3H), 7.79 (d, J = 8.3 Hz, 3H), 7.26 (s, 3H), 7.06 (d,
J = 8.2 Hz, 3H), 2.95–2.90 (m, 6H), 2.95–2.90 (m, 6H), 2.39 (s, 9H), 2.19–2.13 (m, 6H), 0.96–
0.84 (m, 12H), 0.61–0.52 (m, 6H), 0.45 (t, J = 7.3 Hz, 18H), 0.43–0.41 (m, 6H). 13C NMR (126
MHz, CDCl3, 298 K), δ (ppm) 197.37, 153.88, 148.90, 144.85, 144.48, 139.52, 138.19, 137.95,
134.01, 132.25, 129.75, 129.57, 124.57, 123.75, 88.42, 56.10, 36.34, 26.53, 22.68, 20.98, 13.80.
ESI-HRMS (m/z): [M+Na]+ calcd. for C75H81I3O3Na+, 1433.3212; found, 1433.3210.
S4
Synthesis of 5: Compound 4 (2.5 g, 1.7 mmol), palladium (II) acetate (0.05 g, 0.2 mmol),
potassium acetate (1.35 g, 13.8 mmol), and tetrabutylammonium bromide (TBAB, 2.9 g, 9.0
mmol) were mixed in a 50 mL flask. N,N-dimethylformamide (24 mL) was added to the flask. The
reaction was heated at 154 oC in a nitrogen atmosphere and stirred for 36 h. After that, the reaction
was poured into water to get yellow precipitate. The precipitate was collected and dissolved by
dichloromethane (50 mL). The solution was dry over anhydrous sodium sulphate. The crude
product
was
purified
by
column
chromatography
on
silica
gel
with
petroleum
ether/dichloromethane (3:1, v/v) as mobile phase to give 5 (1.1 g, 58%) as a yellow solid. 1H
NMR (500 MHz, CDCl3, 298 K), δ (ppm) 8.50 (s, 3H), 7.79 (s, 3H), 7.59 (d, J = 7.5 Hz, 3H), 7.54
(s, 3H), 7.40 (d, J = 7.4 Hz, 3H), 2.97–2.91 (m, 6H), 2.44 (s, 9H), 2.29–2.23 (m, 6H), 1.00–0.89
(m, 12H), 0.71–0.64 (m, 6H), 0.57–0.52 (m, 6H), 0.48 (t, J = 7.3 Hz, 18H). 13C NMR (126 MHz,
CDCl3, 298 K), δ (ppm) 194.08, 154.61, 148.40, 145.63, 143.76, 142.13, 139.24, 138.13, 135.41,
135.24, 133.37, 125.07, 119.72, 118.27, 116.01, 55.86, 36.61, 26.67, 22.81, 21.44, 13.79.
ESI-HRMS (m/z): [M+Na]+ calcd. for C75H78NaO3+, 1049.5843; found, 1049.5842.
Synthesis of 6: Compound 5 (1.6 g, 1.56 mmol), N-Bromosuccinimide (NBS, 2.5 g, 14.0 mmol),
and azobisisobutyronitrile (AIBN, 0.07 g, 0.43 mmol) were mixed in a 50 mL flask. The flask was
S5
added carbon tetrachloride (32 mL) then degased to change the atmosphere into nitrogen. The
reaction was heated at 80 oC in nitrogen atmosphere and stirred for 36 h under the irradiation of
visible light. After that, the solvent of reaction was removed under vacuum. The residue solid
containing crude product 6 was used without further purification.
Synthesis of 2d: Crude product 6 from former step was mixed with aqueous dimethylamine (20
mL, 40 wt.%) in a 200 mL flask. Tetrahydrofuran (20 mL) and water (7 mL) were added to the
flask. The mixture was heated at 65 oC in nitrogen atmosphere and stirred overnight. The crude
product was extracted by dichloromethane (15 mL) for three times. The organic phase was
combined and washed with brine, then dried over anhydrous sodium sulphate. The crude product
was purified by column chromatography on silica gel with petroleum ether/ethyl acetate (10:1, v/v)
as mobile phase to give 2d (0.67 g, 40% from 5) as a yellow solid. 1H NMR (850 MHz, CDCl3,
298 K), δ 10.09 (s, 3H), 8.67 (s, 3H), 8.23 (s, 3H), 8.19 (d, J = 7.4 Hz, 3H), 7.92 (s, 3H), 7.90 (d, J
= 7.4 Hz, 3H), 3.00–2.96 (m, 6H), 2.35–2.31 (m, 6H), 1.02–0.97 (m, 6H), 0.96–0.91 (m, 6H),
0.96–0.91 (m, 6H), 0.71–0.65 (m, 6H), 0.57–0.52 (m, 6H), 0.49 (t, J = 7.4 Hz, 18H).
13
C NMR
(214 MHz, CDCl3, 298 K), δ = 191.97, 190.58, 156.59, 149.87, 148.88, 145.82, 142.40, 137.94,
137.26, 136.57, 135.66, 134.08, 125.15, 120.33, 118.79, 117.29, 56.20, 36.61, 26.70, 22.77, 13.77.
ESI-HRMS (m/z): [M+Na]+ calcd. for C75H72O6Na+, 1091.5221; found, 1091.5238.
S6
3. The isosurfaces of the Fukui function f –
Figure S1. The isosurface for f – of 1a and the corresponding f – values for C1–C4.
Figure S2. The isosurface for f – of 2a and the corresponding f – values for C1–C4.
S7
4. UV/Vis absorption and fluorescence
Figure S3. UV/Vis absorption spectra of 1a–1c recorded in CH2Cl2 (1 × 10-5 M). The data of 1a
was from the reported work.[2]
Figure S4. UV/Vis absorption spectra of 2a–2d recorded in CH2Cl2 (1 × 10-5 M). The data of 2a
was from the reported work.[2]
S8
Figure S5. Normalized fluorescence spectra of 1a–1c recorded in CH2Cl2 (1 × 10-5 M). The data
of 1a was from the reported work.[2]
Figure S6. Normalized fluorescence spectra of 2a–2d recorded in CH2Cl2 (1 × 10-5 M). The data
of 2a was from the reported work.[2]
S9
Table S1. UV/Vis absorption and fluorescence data of 1a–1c and 2a–2d.
Compound
λonset abs. [nm]
λmax abs. [nm]
λmax em. [nm]
1a[a]
355
338
351, 367[b]
1b
400
360
431
1c
407
361
446
2a[a]
355
340
362, 379[b]
2b
404
361
431
2c
416
362
444
2d
469
414
517
[a] The data of 1a and 2a were from the reported work.[2] [b] Shoulder peaks.
S10
5. X-ray crystallographic analysis
Single crystal X-ray diffraction data were collected on Rigaku SuperNova X-Ray single crystal
diffractometer using CuKα (λ = 1.54184 Å) micro-focus X-ray source. Relatively large crystals
were collected and covered by protective oil. The crystals were mounted on X-ray and kept at 100
K with liquid nitrogen stream during the unit cell determination and full data collection.
The raw data were collected and reduced by CrysAlisPro software. The structures were solved
with the SHELXT and refined with the SHELXL using Least Squares minimization, and Olex2 as
GUI. The detailed crystal parameters are listed in the Supplementary Table S2.
Refinement details: For each crystal, all non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were placed at calculated positions using the riding model and refined
isotropically. The instructions AFIX 23 and AFIX 43 were used for the hydrogen atoms on the
secondary –CH2– and the aromatic C–H, respectively, with the parameter of Uiso = 1.2 Ueq. The
instruction AFIX 33 was used for the hydrogen atoms on the highly disordered terminal –CH3
groups with the parameter of Uiso=1.5 Ueq. No SHELX restraint was applied to the molecular
skeleton. Nevertheless, the flexible butyl groups are expected to be highly disordered, as they are
flexible and vibrate randomly in the crystal. Therefore, necessary SHELX restraints (i.e., DELU,
SIMU, and EADP) were applied to the butyl groups to result in a reasonable model. Specifically,
the anisotropic displacement parameters of disordered atoms in butyl groups were restrained to be
equal within an effective standard deviation of 0.001 using the DELU command. Uij values of
disordered atoms of butyl groups were constrained to be similar using the SIMU command.
Atomic displacement parameters (ADPs) of different parts of disordered atoms were restrained
using the EADP command. There are large voids in crystal, filling with highly disordered solvent
molecules. A satisfactory disorder model for the solvent molecules was not found, therefore the
Olex2 Solvent Mask routine (similar to PLATON/SQUEEZE) was used to mask out the disordered
density.
S11
Table S2. Crystal data and structure refinement.
Compound
2b
2c
Empirical formula
C75H78O3
C75H78O3
Formula weight
1027.37
1027.37
Temperature / K
102(3)
100.0(3)
Crystal system
monoclinic
monoclinic
Space group
I2/a
I2/a
a/Å
22.4535(4)
21.5572(4)
b/Å
20.2319(5)
20.1039(3)
c/Å
26.7671(5)
26.8578(5)
α/°
90
90
β/°
92.304(2)
93.342(2)
90
90
Volume / Å
12149.8(4)
11619.9(4)
Z
8
8
ρcalc g/ cm
1.123
1.175
-1
0.507
0.531
4416.0
4416.0
Crystal size / mm
0.2 ×0.2 × 0.2
0.2 ×0.2 × 0.2
Radiation
CuKα (λ = 1.54184 Å)
CuKα (λ = 1.54184 Å)
2θ range for
data collection / o
5.478 to 147.766
6.016 to 130
Index ranges
-27 ≤ h ≤ 27,
-25 ≤ k ≤ 20,
-17 ≤ l ≤ 33
-25 ≤ h ≤ 25,
-23 ≤ k ≤ 23,
-22 ≤ l ≤ 31
Reflections collected
33967
58765
Independent
reflections
11738 [Rint = 0.0281,
Rsigma = 0.0305]
9838 [Rint = 0.0543,
Rsigma = 0.0380]
Data/restraints/
parameters
11738/44/764
9838/0/728
Goodness-of-fit on F2
1.068
1.092
Final R indexes [I>2σ
(I)]
R1 = 0.0873, R2 = 0.2775
R1 = 0.1068, R2 = 0.2873
Final R indexes [all
data]
R1 = 0.1014, R2 = 0.3000
R1 = 0.1339 R2 = 0.3118
Largest diff. peak/
hole / e Å-3
0.52 / -0.42
0.60 / -0.29
Flack parameter
-
-
CCDC#
2049943
2049944
γ/°
3
-3
μ / mm
F(000)
3
S12
6. Concentration-dependent 1H NMR experiments and the determination of
self-association constants
The determination of self-association constants was performed based on concentration-dependent
1
H NMR experiments using solvent residual peak as an internal standard. The data points were
fitted by the equation from the isodesmic aggregation mode.
In the equation, δm and δa are the chemical shifts of a given compound in free monomer and
aggregates status, respectively, which can be obtained from nonlinear fitting. δexp represents the
chemical shifts from experiments. K is the aggregation association constant and cT is the
concentration of the compound.
Figure S7. Chemical shifts of Ha in 1b under different concentrations (benzene-d6, 400 MHz, 343
K) and the fitting curve of chemical shifts of Ha against concentrations.
S13
Figure S8. Chemical shifts of Hb in 1c under different concentrations (benzene-d6, 400 MHz, 343
K) and the fitting curve of chemical shifts of Hb against concentrations.
Figure S9. 1H NMR spectra of compound 2b under different concentrations (benzene-d6, 400
MHz, 298 K).
S14
Figure S10. 1H NMR spectra of compound 2c under different concentrations (benzene-d6, 850
MHz, 298 K).
Figure S11. 1H NMR spectra of compound 2d under different concentrations (benzene-d6, 850
MHz, 298 K).
S15
7. 1D and 2D NMR spectra
Figure S12. 1H NMR spectrum of 1b (400 MHz, C6D6, 343 K).
Figure S13. 13C NMR spectrum of 1b (101 MHz, C6D6, 343 K).
S16
Figure S14. Heteronuclear singular quantum correlation (HSQC) spectrum of 1b (C6D6, 343 K).
Figure S15. 1H-1H correlation spectroscopy (COSY) spectrum of 1b (C6D6, 343 K).
S17
Figure S16. Nuclear Overhauser effect spectroscopy (NOESY) spectrum of 1b (C6D6, 343 K).
Figure S17. 1H NMR spectrum of 1c (400 MHz, C6D6, 343 K).
S18
Figure S18. 13C NMR spectrum of 1c (101 MHz, C6D6, 343 K).
Figure S19. HSQC spectrum of 1c (C6D6, 343 K).
S19
Figure S20. HSQC spectrum of 1c (C6D6, 343 K).
Figure S21. 1H-1H COSY spectrum of 1c (C6D6, 343 K).
S20
Figure S22. 1H-1H COSY spectrum of 1c (C6D6, 343 K).
Figure S23. NOESY spectrum of 1c (C6D6, 343 K). The signal of proton in FG (Ha) showed
correlation with the signal of the proton in 5-position (Hg), indicating that they were spatially
proximate.
S21
Figure S24. NOESY spectrum of 1c (C6D6, 343 K).
Figure S25. NOESY spectrum of 1c (C6D6, 343 K).
S22
Figure S26. 1H NMR spectrum of 2b (850 MHz, CDCl3, 298 K).
Figure S27. 13C NMR spectrum of 2b (216 MHz, CDCl3, 298 K).
S23
Figure S28. HSQC NMR spectrum of 2b (CDCl3, 298 K).
Figure S29. 1H-1H COSY NMR spectrum of 2b (CDCl3, 298 K).
S24
Figure S30. NOESY NMR spectrum of 2b (CDCl3, 298 K).
Figure S31. 1H NMR spectrum of 2c (850 MHz, CDCl3, 298 K).
S25
Figure S32. 13C NMR spectrum of 2c (214 MHz, CDCl3, 298 K).
Figure S33. HSQC spectrum of 2c (CDCl3, 298 K).
S26
Figure S34. HSQC spectrum of 2c (CDCl3, 298 K).
Figure S35. 1H-1H COSY spectrum of 2c (CDCl3, 298 K).
S27
Figure S36. 1H-1H COSY spectrum of 2c (CDCl3, 298 K).
Figure S37. 1H NMR spectrum of compound 2d (850 MHz, CDCl3, 298 K).
S28
Figure S38. 13C NMR spectrum of compound 2d (214 MHz, CDCl3, 298 K)
Figure S39. 1H NMR spectrum of compound 4 (500 MHz, CDCl3, 298 K)
S29
Figure S40. 13C NMR spectrum of compound 4 (126 MHz, CDCl3, 298 K).
Figure S41. 1H NMR spectrum of compound 5 (500 MHz, CDCl3, 298 K).
S30
Figure S42. 13C NMR spectrum of compound 5 (126 MHz, CDCl3, 298 K).
S31
8.
Reference
[1] Gaussian 09, Revision E.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A.
Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji,
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