1

Supporting Information

Atomic zinc dispersed on graphene synthesized for active CO2 fixation to cyclic carbonates

Congwei Wang,*, a, † Qingwen Song,*, a, † Kan Zhang, a Ping Liu, a Junying Wang, a

Jianmei Wang, b Hengxuan Zhang b and Junzhong Wang a

a CAS Key Laboratory of Carbon Materials, State Key Laboratory of Coal

Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan,

030001, P. R. China.

b Institute of Mining Technology, Key Laboratory of In-situ Property-improving

Mining of Ministry of Education, Taiyuan University of Technology, Taiyuan,

030024，P. R. China.

† These authors contributed equally to this work.

Email: wangcongwei@sxicc.ac.cn; songqingwen@sxicc.ac.cn

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2019

2

Table of Contents

1. General Experimental Methods.............................................................................................2

2. Supplementary Experimental Results ..................................................................................4

3. Characterization Data of the Products .................................................................................6

4. NMR Spectrum of the Products ............................................................................................8

3

1. General Experimental Methods

General materials

Graphite (99.95% purity) was obtained from Qingdao Huarun Graphite Co., Ltd.,

Chemically pure hydrochloric acid (HCl, 37%), sodium oleate (Na-Oleate), oleic acid

(OA), zinc chloride (ZnCl2), cobalt chloride (CoCl2), ferric chloride (FeCl3), ethanol,

hexane and melamine were purchased from Sinopharm Chemical Reagent Co., Ltd.

All aqueous solution was prepared by deionized water. Unless otherwise noted,

carbon dioxide (99.99%) was employed. Commercially available epoxides and

(nCnH2n+1)4NBr (n = 2-4 and 7), 3,4-Epoxytetrahydrofuran (96% purity) and 4-vinyl-

1-cyclohexene-1,2-epoxide (mixture of two isomers, 98% purity) were purchased

from Aladdin and used as received. All reactions were carried out without any special

precautions against air. All chemicals were used without further purification.

Material preparation

The zinc–oleate complex was prepared by reacting zinc chloride and sodium

oleate as described elsewhere.[S1] Briefly, 24 mmol ZnCl2 and 36 mmol sodium oleate

was dissolved in a mixture solvent composed of 18 ml distilled water, 24 ml ethanol,

and 42 ml hexane and 1 mL HCl. The resultant solution was heated to 70 °C and kept

at this temperature for 4 hours under stirring and reflux. The reactant was then washed

with distilled water in a separatory funnel several times and evaporated off hexane,

resulting a thick milk-colored waxy zinc-oleate complex.

In a typical synthesis, 0.2 g electrochemically exfoliated graphene powder was

mixed with 3 mmol zinc-oleate complex, 2 mmol oleic acid and 3 mmol melamine by

using a pestle and mortar. The slurry was then heated to 800 °C at a heating rate of 10

°C min-1 and kept at 800°C for two hours under argon atmosphere in quartz tube

furnace. The product (NG-ZnO) was then washed with 10 % volume ratio HCl

solution and water for the removal of resultant zinc-based nanoparticles for several

times sequentially, and dried at 60°C overnight to give atomic zinc coordinated @

nitrogen doped graphene (NG-aZnN). For comparison, half of zinc-oleate complex

4

was also employed to make NG-aZnN-L (L: low zinc content) by using the same

process.

As control samples, iron-oleate complex and cobalt-oleate complex was also

used to prepare Fe species coordinated @ N doped graphene (NG-Fe) and Co species

coordinated @ N doped graphene (NG-Co) catalyst using the same aforementioned

preparation process.

In order to evaluate the significance of graphene support, sample without the

introduction of graphene was also made as NC-ZnO using the same preparation

process. Moreover, pure graphene (G) and nitrogen doped graphene (NG) was also

prepared and evaluated.

Instrumental characterization

Scanning electron microscopy (SEM) images were obtained on a field-emission

SEM JSM-7001F (FESEM) operating at 10 kV. X-ray diffraction (XRD) was

recorded from 5 to 80° at a scan rate of 0.02° s-1 using the Cu Kα 1.5406 Å radiation.

Transmission electron microscopy (TEM) images were taken with FEI, TECNAI G2

F20 microscopy at acceleration voltage of 200 kV. HAADF-STEM was performed on

a JEM ARM200F equipped with double aberration correctors in Institute of physics,

Chinese Academy of Sciences, and a cold field emission gun operated at 200 kV.

STEM images were recorded using a HAADF detector with a convergence angle of

25 mrad and a collection angle between 70 and 250 mrad. Under these conditions, the

spatial resolution is ca. 0.08 nm. X-ray photoelectron spectroscopy (XPS)

measurements were performed using Thermo ESCALAB 250 spectrometer,

employing an Al-KR X-ray source with a 500 μm electron beam spot. The

Brunauer−Emmett−Teller (BET) specific surface area was deduced from the N2

physical adsorption measurement data that were obtained using an ASAP 2010

Accelerated Surface Area and Porosimetry System. X-ray absorption near-edge

structure (XANES) measurements at Zn K-edge in transmission mode were

performed at the BL14W1 in Shanghai Synchrotron Radiation Facility. The electron

beam energy was 3.5 GeV and the stored current was 230 mA (top-up). The raw data

5

analysis was performed using IFEFFIT software package according to the standard

data analysis procedures. 1H NMR spectra was recorded on Bruker AVANCE III 400

MHz spectrometers using CDCl3 as solvent referenced to CDCl3 (7.26 ppm). 13C

NMR was recorded at 100.6 MHz in CDCl3 (77.00 ppm). Multiplets were assigned as

singlet, doublet, triplet, doublet of doublet, multiplet and broad singlet. High

resolution mass spectrometry was conducted using a Bruker micrOTOF-Q III by ESI

technique.

Procedure for the cycloaddition of CO2 and propylene oxide according to the following Scheme

+ O O

O

H3C

CO2CatalystO

H3C

1a 2a

Take cycloaddition of CO2 with propylene oxide 1a as an example: the reaction

was carried out in a stainless steel autoclave (50 cm3 inner volume) with a stir bar.

NG-aZn (15 mg, 0.12 mol%Zn content on the basis of substrate 1), (nC7H15)4NBr

(49.1 mg, 0.5 mol%) and propylene oxide (1.40 mL, 20 mmol) was successively

introduced and sealed at zero temperature (ice-water mixture). The pressure was

adjusted to 1 MPa at the preset temperature and the autoclave was heated at that

temperature for the preset time. After the reaction was completed, the reactor was

cooled in ice-water bath, and then excess of CO2 was carefully vented. The mixture

was diluted with ethyl acetate, and the yield of cyclic carbonate was determined by

gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m ×

0.25 μm) using a flame ionization detector using biphenyl (0.20 g) as the internal

standard. Then, the residue was obtained by removing the solvent under vacuum and

further purified by column chromatography with ethyl acetate-petroleum ether as the

eluent to obtain the desired product. All cyclic carbonates have been reported

previously and the characterization data are all in good agreement with literature

value.

6

2. Supplementary Experimental Results

(a) (b)

Fig. S1 TEM images of electrochemically exfoliated graphene sheets.

(a) (b)

Fig. S2 TEM images of intermediate product of NG-ZnO.

7

600 900 1200 1500 1800

G

NG-aZnN

Inte

nsity

(a.u

.)

Wavenumber (cm-1)

Graphene

D

Fig. S3 Raman spectra of graphene and NG-aZnN.

Fig, S3 shows the Raman spectra of graphene and NG-aZnN, in which D (~1340

cm-1) and G (~1560 cm-1) peaks reflect the population of structural defects and the

index of graphitization, respectively. The extent of defects could be quantified by

calculating the relative intensities of these two peaks (ID/IG). It is clearly shown that

after the thermal pyrolysis, NG-aZnN own more introduced defects, which could

benefit for the anchoring and stabilization of atomic Zn atoms.

(a) (b)

Fig. S4 SEM images of (a) directly pyrolyzed NG-ZnO and (b) acid washed NG-aZn.

8

(a) (b)

Fig. S5 (a) high-angle annular dark field image of NG-aZnN and (b) corresponding

bright-field STEM image, the bright spots on left and dark spots on right are

corresponding to isolated Zn atoms.

2 4 6 8 10

k3 (k

)

k (Å-1)

ZnO Fitting

0 2 4 6

IFT k3

(k

)I (Å

-4)

R ( Å)

ZnO Fitting

2 4 6 8 10 12

Zn Foil Fitting

k3 (k

)

k (Å-1)0 2 4 6 8 10

IFT k3

(k

)I (Å

-4)

R ( Å)

Zn Foil Fitting

(a) (b)

(c) (d)

Fig. S6 Fourier transform k3-weighted χ (k)-function of the EXAFS spectra of

metallic Zn foil and ZnO and corresponding first shell fitting at (a, c) R space and (b,

d) k space.

9

1020 1025 1030 1035

NG-aZnNIn

tens

ity (a

.u.)

Binding energy (eV)

NG-ZnO

Zn 2p3/2

20 30 40 50 60 70

NG-ZnO

NG-aZnN

Inte

nsity

(a.u

.)

2theta (degree)

Raw G

1000 800 600 400 200 0

Zn A

uger

Zn 2p

O 1

s

C 1s

N 1s

Zn 3

sZn

3p

NG-ZnO

Inte

nsity

(a.u

.)

Binding energy (eV)

Zn 3

d

NG-aZnN

0.0 0.2 0.4 0.6 0.8 1.00

50

100

150

200

250

300

1 10 1000.000.050.100.150.200.250.300.35

Qua

ntity

ads

orbe

d (c

m3 /g

)

Relative pressure (P/P0)

Graphene NG-aZnN

dV/d

log(

D) (c

m3 g-1

nm-1)

Pore width (nm)

(a) (b)

(c) (d)

Fig. S7 (a) XRD patterns of graphene, NG-ZnO and NG-aZnN, (b) N2

adsorption/desorption isotherm of graphene and NG-aZnN, inset pore size

distributions, (c) Long range XPS spectra of NG-ZnO and NG-aZnN, (d) spectra of

Zn 2p3/2 region for NG-ZnO and NG-aZnN.

295 290 285 280

C-N

C=O

Inte

nsity

(a.u

.)

Binding energy (eV)

C-C

408 405 402 399 396 393

Graphitic N

N-oxide Zn-N

Pyridinic N

Inte

nsity

(a.u

.)

Binding energy (eV)

(a) (b)

Fig. S8 The XPS spectra of (a) C 1s and (b) N 1s of NG-aZnN with the deconvolution.

10

Fig. S9 Investigation of temperature effect on the cycloaddition of CO2 and propylene

oxide. a

aReaction conditions: propylene oxide (1.16 g, 20 mmol), NG-aZnN (15 mg),

(nC7H15)4NBr (0.5 mol%), 1 MPa CO2, 1 h. bGC yield.

Fig. S10 aReaction conditions: propylene oxide (1.16 g, 20 mmol), NG-aZnN (15 mg), (nC7H15)4NBr (0.5 mol%), 120 oC, 1 h. bGC yield.

11

1 2 30

20

40

60

80

100

Conv

ersio

n (%

)

Recycle run

Yield Selectivity

Fig. S11 Recyclability of NG-aZnN for cycloaddition of CO2 and propylene oxide

under 120 °C, 1 MPa, 3 h.

Atomic dispersed Zn

Zn atom aggregation

Fig. S12 HAADF image of NG-aZnN after the recyclability test.

12

Table S1. Element compositions obtained XPS.

Sample C (at. %) N (at. %) Zn (at. %) O (at. %)

NG-ZnO 70.93 11.13 8.62 9.32

NG-aZnN 78.41 10.11 1.57 9.91

Table S2. Element compositions obtained via ICP-OES (Zn) and elemental analysis

(C/N/O)

Sample C (at. %) N (at. %) Zn (at. %) O (at. %)

NG-ZnO 75.09 12.09 3.99 8.83

NG-aZnN 85.07 9.11 1.62 4.2

Table S3. EXAFS fitting obtained via IFEFFIT software package.

Sample Path N R(Å) σ 2 (×10

-2 Å

2 ) ΔE

0 (eV) R-factor

Zn Foil Zn-Zn 6 2.64 1.55 3.18 0.08

Zn-O 1 1 1.97 0.01ZnO

Zn-O 2 3 2.07 6.23.13 0.05

NG-aZnN Zn-N 3.76 2.01 0.83 1.87 0.006

13

Table S4. Effect of Reaction Parameters on the Cycloaddition of CO2 and Propylene

Oxide a

+ O O

O

H3C

CO2CatalystO

H3C

1a 2a

Entry Catalyst Co-catalyst T(°C) P(MPa) Time (h) Yield (%) b

1 - nPr4NBr 120 1 2 18.1

2 Graphene nPr4NBr 120 1 2 41.5

3 NG-aZnN nPr4NBr 120 1 2 75.5

4 NG-aZnN Et4NBr 120 1 2 61.5

5 NG-aZnN nBu4NBr 120 1 2 83.8

6 NG-aZnN (nC7H15)4NBr 120 1 2 94.6

7 NG-aZnN (nC7H15)4NBr 120 1 3 >99(85) c

8 NG-aZnN (nC7H15)4NBr 160 1 1 84.1

9 NG-aZnN (nC7H15)4NBr 160 3 1 97.9(96) c

10 NG-aZnN (nC7H15)4NBr 160 3 0.5 91.7

a Reaction conditions: propylene oxide (1.16 g, 20 mmol), or NG-aZnN (15 mg), nR4NX (0.5

mol%). b Determined by GC using biphenyl as the internal standard. c Recovered catalyst for the

second run.

14

3. Characterization Data of the Products

2aO

O

O

H3C

4-Methyl-1,3-dioxolan-2-one (2a) Colorless liquid. 1H NMR (CDCl3, 400 MHz) δ 4.84-4.92 (m, 1H), 4.58 (t, J = 8.4 Hz, 1H), 4.04 (t, J = 8.4 Hz, 1H), 1.49 (d, J = 6.0 Hz, 3H) ppm. 13C NMR (CDCl3, 100.6 MHz) δ 155.1, 73.7, 70.7, 19.4 ppm.

2bO

O

O

Et

4-Ethyl-1,3-dioxolan-2-one (2b) Colorless liquid. 1H NMR (CDCl3, 400 MHz) δ 4.62-4.69 (m, 1H), 4.51 (t, J = 8.2 Hz, 1H), 4.05-4.09 (1H), 1.68-1.86 (m, 2H), 1.01 (t, J = 7.6 Hz, 3H) ppm. 13C NMR (CDCl3, 100.6 MHz) δ 155.1, 78.0 , 69.0, 26.9, 8.4 ppm.

2cO

O

O

nBu

4-n-Butyl-1,3-dioxolan-2-one (2c) Colorless liquid. 1H NMR (CDCl3, 400 MHz) δ 4.66-4.73 (m, 1H), 4.52 (t, J = 8.0 Hz, 1H), 4.06 (dd, J = 7.3 Hz, J = 8.0 Hz, 1H), 1.63-1.85 (m, 2H), 1.30-1.49 (m, 4H), 0.92 (t, J = 7.0 Hz, 3H) ppm. 13C NMR (CDCl3, 100.6 MHz) δ 155.1, 77.0, 69.4, 33.5, 26.4, 22.2, 13.8 ppm.

2dO

O

O

Ph

4-Phenyl-1,3-dioxolan-2-one (2d) White solid. 1H NMR (CDCl3, 400 MHz) δ 7.44 (d, 3J = 6.4 Hz, 3H), 7.36 (d, J = 7.6 Hz, 2H), 5.70 (t, J = 8.0 Hz, 1H), 4.80 (t, J = 8.4 Hz, 1H), 4.35 (t, J = 8.4 Hz, 1H) ppm. 13C NMR (CDCl3, 100.6 MHz) δ 157.7, 154.7, 129.6, 121.9, 114.6, 74.1, 68.8 66.2 ppm.

2e

OO

O

O

4-i-Propoxy-1,3-dioxolan-2-one (2e) Colorless liquid. 1H NMR (CDCl3, 400 MHz) δ 4.82 (m, 1H), 4.50 (t, J = 8.0 Hz, 1H), 4.38 (dd, J = 8.0 Hz, J = 15.6 Hz, 1H), 3.58–3.70 (m, 3H), 1.16 (t, J = 6.4 Hz, 6H) ppm. 13C NMR (CDCl3, 100.6 MHz) δ 155.2, 75.3, 72.9, 67.1, 66.4, 21.9, 21.8 ppm.

2f

OO

O

O

4-((Allyloxy)methyl)-1,3-dioxolan-2-one (2f) Colorless liquid. 1H NMR (CDCl3, 400 MHz) δ 5.81-5.91 (m, 1H), 5.20-5.30 (m, 2H), 4.79-4.84 (m, 1H), 4.37-4.52 (m, 2H), 4.03-4.06 (m, 2H),

15

3.59-3.70 (m, 2H) ppm. 13C NMR (CDCl3, 100.6 MHz) δ 154.9, 133.6, 117.9, 75.0, 72.6, 68.8, 66.2 ppm.

2gO

O

O

OPh

4-Phenoxymethyl-1,3-dioxolan-2-one (2g) White solid, mp: 99-100 oC. 1H NMR (CDCl3, 400 MHz) δ 7.31 (t, J = 8.0 Hz, 2H), 7.02 (t, J = 7.4 Hz, 1H), 6.91 (d, J = 8.0 Hz, 2H), 5.02-5.04 (m, 1H), 4.62 (t, J = 8.4 Hz, 1H), 4.55 (dd, J = 8.4 Hz, J = 6.0 Hz, 1H), 4.24 (dd, J = 3.6 Hz, J = 10.8 Hz, 1H), 4.16 (dd, J = 4.4 Hz, J = 10.8 Hz, 1H) ppm. 13C NMR (CDCl3, 100.6 MHz) δ 157.8, 129.7, 122.1, 114.7, 74.1, 66.9, 66.3 ppm.

2h

OO

O

Hexahydrobenzo[1,3]dioxol-2-one (2h) Slight yellow liquid. 1H NMR (CDCl3, 400 MHz) δ 4.67 (m, 2H), 1.88 (d, J = 5.4 Hz, 4H), 1.56-1.65 (m, 2H), 1.36-1.45 (m, 2H) ppm. 13C NMR (CDCl3, 100.6 MHz) δ 155.3, 75.7, 26.7, 19.1 ppm.

OO

O

O

2i

Tetrahydrofuro[3,4-d][1,3]dioxol-2-one (2i) White solid. 1H NMR (CDCl3, 400 MHz) δ 5.17-5.21 (m, 2H), 4.18 (d, 2H), 3.49-3.55 (m, 2H) ppm. 13C NMR (CDCl3, 100.6 MHz) δ 154.4, 80.1, 72.8 ppm. HRMS (ESI): C5H6O4Na+ for [M+Na]+ calculated 153.0158, found 153.0154.

OO

O

2j

5-Vinylhexahydrobenzo[d][1,3]dioxol-2-one (2j) (mixture of isomers) Colorless liquid. 1H NMR (CDCl3, 400 MHz) δ 5.67-5.78 (m, 1H), 4.98-5.07 (m, 2H), 4.62-4.80 (m, 2H), 1.96-2.35 (m, 3H), 1.53-1.83 (m, 3H), 1.12-1.40 (m, 1H) ppm. 13C NMR (CDCl3, 100.6 MHz) δ 155.1, 140.9 (140.8), 114.3 (114.0), 75.6 (75.5), 75.1, 36.4, 33.8 (33.5), 31.6, 26.6, 25.8 (25.7), 25.0 ppm. HRMS (ESI): C9H12NaO3

+ for [M+Na]+ calculated 191.0679, found 191.0695.

4. NMR Spectrum of the Products

16

2a 1H NMR (CDCl3, 400 MHz)O

O

O

H3C

0.01.02.03.04.05.06.07.08.09.010.0(ppm)

3.00

1.00

1.00

1.00

-0.0

6

1.43

1.44

3.96

3.98

3.99

4.00

4.50

4.52

4.54

4.78

4.80

4.80

4.81

4.81

4.83

4.83

4.85

4.86

7.26

2a1H NMR (CDCl3, 400 MHz)

2a 13C NMR (CDCl3, 100.6 MHz)O

O

O

H3C

0102030405060708090110130150170190(ppm)

19.1

9

70.5

473

.49

76.6

877

.00

77.3

2

154.

96

2a13

C NMR (CDCl3, 100.6 MHz)

2b 1H NMR (CDCl3, 400 MHz)O

O

O

Et

17

012345678910ppm

3.11

2.13

1.03

1.02

1.00

0.99

1.01

1.03

1.73

1.75

1.75

1.77

1.79

1.80

1.82

4.05

4.07

4.07

4.09

4.49

4.51

4.53

4.62

4.63

4.64

4.65

4.65

4.66

4.67

4.67

4.69

7.26

2b 13C NMR (CDCl3, 100.6 MHz)O

O

O

Et

020406080100120140160180200ppm

8.41

26.8

5

68.9

676

.68

77.0

077

.32

77.9

6

155.

08

2c 1H NMR (CDCl3, 400 MHz)O

O

O

nBu

18

012345678910ppm

3.07

4.07

1.12

1.06

1.02

1.01

1.00

0.90

0.92

0.93

1.34

1.35

1.35

1.35

1.36

1.36

1.37

1.38

1.38

1.39

1.39

1.41

1.41

1.43

1.43

1.45

1.67

1.67

1.68

1.69

1.71

1.77

1.79

1.79

1.81

1.81

4.04

4.06

4.06

4.08

4.50

4.52

4.54

4.66

4.68

4.68

4.69

4.70

4.71

4.72

7.26

2c 13C NMR (CDCl3, 100.6 MHz)O

O

O

nBu

020406080100120140160180200ppm

13.7

622

.21

26.3

933

.52

69.3

676

.68

77.0

077

.02

77.3

2

155.

07

2d 1H NMR (CDCl3, 400 MHz)O

O

O

Ph

19

0.51.52.53.54.55.56.57.58.59.5(ppm)

1.01

1.00

0.98

1.98

3.02

0.00

4.29

4.31

4.33

4.76

4.78

4.80

5.64

5.66

5.68

7.34

7.34

7.35

7.35

7.41

7.41

7.42

7.44

2d1H NMR (CDCl3, 400 MHz)

2d 13C NMR (CDCl3, 100.6 MHz)O

O

O

Ph

0102030405060708090110130150170190(ppm)

71.0

276

.68

77.0

077

.32

77.8

6

125.

7612

9.01

129.

5113

5.64

154.

79

2e 1H NMR (CDCl3, 400 MHz)

OO

O

O

20

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5(ppm)

6.09

3.03

0.98

1.00

0.97

1.10

1.11

3.52

3.53

3.55

3.56

3.58

3.59

3.60

3.61

3.62

3.63

3.64

4.31

4.32

4.33

4.34

4.42

4.44

4.47

4.74

4.75

4.75

4.75

4.76

4.76

4.77

7.26

2e 13C NMR (CDCl3, 100.6 MHz)

OO

O

O

0102030405060708090110130150170190(ppm)

21.6

021

.72

66.2

566

.95

72.7

175

.16

76.6

877

.00

77.3

2

155.

03

2f 1H NMR (CDCl3, 400 MHz)

OO

O

O

21

0123456789ppm

2.12

2.08

1.04

1.04

1.01

2.04

1.00

3.59

3.60

3.62

3.63

3.67

3.68

3.69

3.70

4.03

4.04

4.04

4.04

4.05

4.05

4.05

4.06

4.06

4.37

4.39

4.39

4.41

4.47

4.50

4.52

4.80

4.81

4.81

4.81

4.82

4.84

5.20

5.20

5.23

5.23

5.23

5.25

5.26

5.30

5.30

5.82

5.85

5.87

5.89

7.26

2f 13C NMR (CDCl3, 100.6 MHz)

OO

O

O

020406080100120140160180200ppm

66.2

368

.77

72.5

574

.97

76.6

877

.00

77.3

2

117.

92

133.

59

154.

90

2g 1H NMR (CDCl3, 400 MHz)O

O

O

OPh

22

0.51.52.53.54.55.56.57.58.59.5(ppm)

1.00

1.02

1.00

1.02

1.00

1.95

1.01

2.00

4.14

4.15

4.17

4.18

4.22

4.24

4.25

4.26

4.52

4.54

4.54

4.56

4.60

4.62

4.64

5.02

5.02

5.03

5.03

5.04

5.04

6.91

6.92

7.02

7.04

7.26

7.29

7.31

7.31

7.33

2g1H NMR (CDCl3, 400 MHz)

2g 13C NMR (CDCl3, 100.6 MHz)O

O

O

OPh

0102030405060708090110130150170190(ppm)

66.2

466

.92

74.0

476

.68

77.0

077

.32

114.

6412

2.04

129.

70

157.

77

2h 1H NMR (CDCl3, 400 MHz)

OO

O

23

12345678ppm

2.14

2.18

4.20

2.00

1.38

1.39

1.39

1.40

1.41

1.42

1.43

1.44

1.45

1.56

1.58

1.60

1.61

1.62

1.62

1.63

1.65

1.86

1.87

1.88

1.89

1.90

4.66

4.66

4.67

4.67

4.68

4.68

7.26

2h 13C NMR (CDCl3, 100.6 MHz)

OO

O

020406080100120140160180200ppm

19.0

9

26.6

9

75.7

076

.68

77.0

077

.32

155.

33

2i 1H and 13C NMR

OO

O

O

24

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5(ppm)

2.00

2.00

1.96

3.49

3.50

3.51

3.51

3.53

3.53

3.54

3.54

3.55

4.16

4.19

5.17

5.18

5.19

5.19

5.19

5.21

7.26

0102030405060708090110130150170190(ppm)

72.7

776

.68

77.0

077

.32

80.0

7

154.

43

2j (mixture of isomers) 1H and 13C NMR

OO

O

25

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5(ppm)

1.47

3.04

3.18

2.00

2.01

1.00

1.16

1.18

1.37

1.56

1.57

1.60

1.60

1.64

1.65

1.66

1.67

1.67

1.68

1.69

1.69

2.24

2.24

2.28

2.31

2.32

2.34

2.34

2.35

4.63

4.65

4.67

4.70

4.77

4.78

4.79

4.98

4.98

5.00

5.00

5.01

5.01

5.02

5.04

5.04

5.06

5.07

5.70

5.72

5.74

0102030405060708090110130150170190(ppm)

24.9

925

.67

25.7

526

.63

31.6

333

.49

33.8

236

.35

75.0

775

.54

75.5

675

.91

76.6

877

.00

77.3

2

113.

9711

4.25

140.

8214

0.90

155.

0715

5.10

Reference[S1] Wang, C.; Zhang, H.; Zhang, Y.; Cheng, M.; Zhao, H.; Wang, J. Chem. Mater. 2017, 29, 9915-9922.