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Electronic Supplementary Information (ESI) for

Stereoselective photoreaction in P-stereogenic

dithiazolylbenzo[b]phosphole chalcogenides

Shunsuke Iijima,a Takuya Nakashimaa and Tsuyoshi Kawaia,b*

a Graduate School of Materials Science, Nara Institute of Science and Technology, NAIST, 8916-5

Takayama, Ikoma, Nara, 630-0192, Japan.

E mail: tkawai@ms.naist.jp

b NAIST-CEMES International Collaborative Laboratory for Supraphotoactive System, Centre

d’Élaboration de Matériaux et d’Etudes Structurales, CEMES,

29, rue Jeanne Marvig, BP 94347, Toulouse 31055, France.

Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016

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1. NMR characterizations

Fig. S1 1H NMR spectrum of rac-1a in CDCl3.

Fig. S2 13C NMR spectrum of rac-1a in CDCl3.

S3

Fig. S3 31P NMR spectrum of rac-1a in CDCl3.

Fig. S4 1H NMR spectrum of rac-2a in CDCl3.

20151126 BPPS-2PTA CDCl3 1H-1-1.jdf

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0

Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

6.003.099.832.213.91

a

a b

b

b

b

ｃ

ｃ

ｃ ｃ

ｃ

ｃ

d

ef

gh

h

h

i

i

a

20151126 BPPS-2PTA CDCl3 1H-1-1.jdf

8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9

Chemical Shift (ppm)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Norm

alized Inte

nsity

3.099.832.213.91

b

e

c, h, f

g, i

d

S4

Fig. S5 13C NMR spectrum of rac-2a in CDCl3.

Fig. S6 31P NMR spectrum of rac-1a in CDCl3.

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2. Photoreaction monitored with UV-vis spectra and 1H NMR

2.1. UV-Vis absorption spectral change

Fig. S7 Changes in the UV-vis absorption spectra of open form (rac-1a, blue solid line) to PSS (red

dashed line), and closed form (1b, red solid line) in toluene (1.9 × 10-5 M).

Fig. S8 Changes in the UV-Vis absorption spectra of open form (rac-1a, blue solid line) to PSS (red

dashed line), and closed form (1b, red solid line) in methanol (2.3 × 10-5 M).

0.8

0.6

0.4

0.2

0.0

Ab

so

rban

ce

700600500400300

Wavelength / nm

1.0

0.8

0.6

0.4

0.2

0.0

Ab

so

rban

ce

700600500400300

Wavelength / nm

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Fig. S9 Changes in the UV-Vis absorption spectra of open form (rac-2a, blue solid line) to PSS (red

dashed line), and closed form (2b, red solid line) in toluene (2.9 × 10-5 M).

Fig. S10 Changes in the UV-Vis absorption spectra of open form (rac-2a, blue solid line) to PSS (red

dashed line), and closed form (2b, red solid line) in methanol (2.8 × 10-5 M).

1.0

0.8

0.6

0.4

0.2

0.0

Ab

so

rban

ce

700600500400300

Wavelength / nm

1.2

0.8

0.4

0.0

Ab

so

rban

ce

700600500400300

Wavelength / nm

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2.2. 1H NMR spectral change

Fig. S11 1H NMR spectrum of photoproducts 1b prepared by UV irradiation to the toluene solution

followed by the separated with RP-HPLC (measured in CDCl3).

Fig. S12 1H NMR spectrum of photoproducts 1b prepared by UV irradiation to the methanol solution

followed by the separated with RP-HPLC (measured in CDCl3).

20150317 BPPO-2PTA-CF from PSS in chloroform CDCl3 1H-1-1.jdf

8 7 6 5 4 3 2 1 0

Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

Norm

alized Inte

nsity

2.350.620.622.3810.194.831.732.08

TMS

-0.0

20

.00

0.1

4

1.2

4

1.5

61

.82

2.0

52

.07

7.2

5

7.4

47

.46

7.5

17

.54

7.9

48

.03

8.0

5

20150317 BPPO-2PTA-CF from PSS in chloroform CDCl3 1H-1-1.jdf

2.15 2.10 2.05 2.00 1.95 1.90 1.85 1.80 1.75

Chemical Shift (ppm)

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

0.11

Norm

alized Inte

nsity

2.350.620.622.38

1.8

2

1.8

6

2.0

5

2.0

7

20150331 BPPO-2PTA-CF from PSS in toluene CDCl3 1H-1-1.jdf

9 8 7 6 5 4 3 2 1 0

Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

Norm

alized Inte

nsity

3.003.1310.854.861.602.131.09

TMS

-0.0

20

.00

1.6

11

.82

1.8

62

.07

7.2

57

.25

7.4

57

.53

7.5

47

.94

7.9

47

.96

8.0

48

.81

20150331 BPPO-2PTA-CF from PSS in toluene CDCl3 1H-1-1.jdf

2.20 2.15 2.10 2.05 2.00 1.95 1.90 1.85 1.80 1.75 1.70 1.65

Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

Norm

alized Inte

nsity

2.911.000.962.99

1.8

2

1.8

6

2.0

02.0

5

2.0

7

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Fig. S13 1H NMR spectrum of photoproducts 2b prepared by UV irradiation to the toluene solution

followed by the separated with RP-HPLC (measured in CDCl3).

Fig. S14 1H NMR spectrum of photoproducts 2b prepared by UV irradiation to the methanol solution

followed by the separated with RP-HPLC (measured in CDCl3).

20150331 BPPO-2PTA-CF from PSS in methanol CDCl3 1H-1-1.jdf

8 7 6 5 4 3 2 1 0

Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

Norm

alized Inte

nsity

2.993.0310.145.131.562.151.21

TMS

0.0

00

.06

1.5

61

.57

1.5

81

.82

1.8

62.0

7

7.2

57

.44

7.4

67

.53

7.5

47

.94

8.0

38

.04

20150331 BPPO-2PTA-CF from PSS in methanol CDCl3 1H-1-1.jdf

2.25 2.20 2.15 2.10 2.05 2.00 1.95 1.90 1.85 1.80 1.75

Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

Norm

alized Inte

nsity

2.281.011.002.34

1.8

2

1.8

6

2.0

5

2.0

7

20151201 BPPS-2PTA-PSSinToluene CDCl3 1H-1-1.jdf

8 7 6 5 4 3 2 1 0

Chemical Shift (ppm)

0

0.05

0.10

0.15

Norm

alized Inte

nsity

5.511.131.005.3433.8524.522.887.064.604.842.36

-0.0

1

1.2

4

1.5

6

1.8

32

.00

2.0

82

.17

2.3

5

3.4

8

7.1

37.1

57.1

67

.18

7.2

37

.25

7.2

7

7.4

57

.94

7.9

47

.96

8.0

38

.04

20151201 BPPS-2PTA-PSSinToluene CDCl3 1H-1-1.jdf

2.10 2.05 2.00 1.95 1.90 1.85 1.80

Chemical Shift (ppm)

0

0.005

0.010

0.015

0.020

0.025

0.030

0.035

0.040

0.045

0.050

0.055

0.060

0.065

Norm

alized Inte

nsity

5.511.131.005.34

1.8

3

1.8

8

1.9

9

2.0

0

2.0

1

2.0

6

2.0

8

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3. Chiral separation

Fig. S15 Chiral HPLC chromatogram of rac-1a in ethanol. (Flow rate: 6 mL / min., Detection

wavelength: 254 nm)

Fig. S16 Chiral HPLC chromatogram of a) primary fraction and b) second fraction separated of rac-

1a in ethanol, after optical resolution. (Flow rate: 6 mL / min., Detection wavelength: 254 nm)

Fig. S17 Chiral HPLC chromatogram of rac-2a in ethanol. (Flow rate: 6 mL / min., Detection

wavelength: 254 nm)

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Fig. S18 Chiral HPLC chromatogram of a) primary fraction and b) second fraction separated of rac-

2a in ethanol, after optical resolution. (Flow rate: 6 mL / min., Detection wavelength: 254 nm)

Fig. S19 CD spectra for rac-1a of open form in toluene (blue: first fraction, red: second fraction).

Fig. S20 CD spectra at PSS states achieved by UV irradiation to the solution in Fig. S15 in toluene.

-10

0

10

CD

/ m

deg

700600500400300

wavelength / nm

-10

0

10

CD

/ m

deg

700600500400300

wavelength / nm

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Fig. S21 CD spectra for rac-2a of open form in toluene (blue: first fraction, red: second fraction).

Fig. S22 CD spectra at PSS states achieved by UV irradiation to the solution in Fig. S17 in toluene.

Fig. S23 CD spectra for rac-2a of open form in methanol (blue: first fraction, red: second fraction).

-20

-10

0

10

20C

D /

md

eg

700600500400300

wavelength / nm

-20

-10

0

10

20

CD

/ m

deg

700600500400300

wavelength / nm

20

10

0

-10

-20

CD

/ m

deg

700600500400300

wavelength / nm

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Fig. S24 CD spectra at PSS states achieved by UV irradiation to the solution in Fig. S19 in methanol.

-20

0

20C

D /

md

eg

700600500400300

wavelength / nm

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4. Study in crystalline state

4.1 Photochromism in crystal

Fig. S25 Photochromism of rac-1a in crystal; (a) before and after (b,c) UV irradiation.

Fig. S26 Photochromism of rac-2a in crystal; (a) before and after (b,c) UV irradiation.

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Fig. S27 1H NMR spectrum of photoproducts prepared by UV irradiation to single crystals 1a and

dissolved in CDCl3.

Fig. S28 1H NMR spectrum of photoproducts prepared by UV irradiation to single crystals 1b and

dissolved in CDCl3.

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4.2 X-ray crystallographic data

Table S1. Crystallographic data for rac-1a and rac-2a

Molecule rac-1a rac-2a

Formula C34H25N2OPS2 C36H28N3PS3

Mol weight (g mol-1) 572.68 629.79

Crystal dimension (mm) 0.100 × 0.070 × 0.020 0.140 × 0.100 × 0.050

Crystal system Monoclinic Triclinic

Space group P21/c (#14) P1̅ (#2)

a (Å) 11.4597(2) 10.0101(2)

b (Å) 29.0720(5) 11.0471(2)

c (Å) 16.6209(3) 14.5019(3)

(°) 86.1262(7)

(°) 93.7884(7) 83.4645(7)

(°) 81.5450(7)

V (Å3) 5525.24(17) 1573.81(5)

Z value 8 2

Dcalcd (g mol-1 ) 1.377 1.329

F (0 0 0) 2384.00 656.00

(Mo K) (cm-1) 2.825 3.171

Temperature (K) 123 123

No. of measured reflections 95332 27280

No. of unique reflections 12666 7207

Goodness of fit 1.05 1.09

Final R indices

R1 0.0395 0.0374

wR2 [I > 2(I)] 0.0997 0.1026

CCDC No. CCDC-1445542 CCDC-1445543

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5. Computational data

Optimization of molecular conformations of 1a and 2a were carried out by DFT calculation with

B97XD/6-31G(d,p) level.

5.1. Optimization of molecular conformation

Fig. S29 Optimized structure of SP-P-1a.

Fig. S30 Optimized structure of SP-M-1a.

CH/N : 2.488 Å

N-P distance : 3.2385 Å

N-O distance : 3.726 Å

CH/ : 3.494 Å CH/ : 3.093 Å

C-C distance : 3.563 Å

CH/ : 3.037 Å

CH/N : 2.400 Å

N-P distance : 3.261 Å

N-O distance : 3.366 Å

CH/ : 6.099 Å

CH/ : 3.114 Å

C-C distance : 3.564 Å

CH/ : 2.995 Å

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Fig. S31 Optimized structure of RP-P-1a.

Fig. S32 Result of optimization of RP-M-1a.

CH/N : 2.500 Å

N-P distance : 3.261 Å

N-O distance : 3.366 Å

CH/ : 6.099 Å CH/ : 2.995 Å

C-C distance : 3.564 Å

CH/ : 3.115 Å

CH/N : 2.488 Å

N-P distance : 3.238 Å

N-O distance : 3.726 Å CH/ : 3.494 Å

CH/ : 3.036 Å C-C distance : 3.563 Å

CH/ : 3.093 Å

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Fig. S33 Optimized structure of SP-P-2a.

Fig. S34 Optimized structure of SP-M-2a.

CH/N : 2.538 Å

N-P distance : 3.112 Å

N-S distance : 3.804 Å

CH/ : 3.552 Å CH/ : 3.253 Å

C-C distance : 3.548 Å

CH/ : 3.061 Å

N-P distance : 3.332 Å

N-S distance : 3.657 Å

CH/ : 6.313 Å

CH/N : 2.505 Å

CH/ : 3.055 Å

C-C distance : 3.590 Å

CH/ : 3.096 Å

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Fig. S35 Optimized structure of RP-P-2a.

Fig. S36 Optimized structure of RP-M-2a.

CH/N : 2.505 Å

N-P distance : 3.332 Å

N-S distance : 3.657 Å

CH/ : 6.311 Å CH/ : 3.054 Å

C-C distance : 3.590 Å

CH/ : 3.0965 Å

CH/N : 2.538 Å

N-P distance : 3.112 Å

N-S distance : 3.804 Å CH/ : 3.552 Å

CH/ : 3.465 Å

C-C distance : 3.548 Å CH/ : 3.193 Å

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5.2. Energy difference between P- and M-conformers estimated by DFT

Fig. S37 Diagram of energy difference between SP-P-1a and SP-M-1a optimized by B97XD/6-

31G(d,p) level of DFT calculation.

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Fig. S38 Diagram of energy difference between SP-P-2a and SP-M-2a optimized by B97XD/6-

31G(d,p) level of DFT calculation.

Fig. S39 Diagram of energy difference between diastereomers of SP-(R,R)-1b and SP-(S,S)-1b

calculated by CAM-B3LYP/6-31G(d,p) level of DFT calculation.

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6. Other NMR data

Fig. S40 1H NMR spectrum of rac-1a in toluene-d8.

Fig. S41 1H NMR spectrum of rac-2a in toluene-d8.

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Fig. S42 31P NMR spectrum of rac-1a in toluene-d8.

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Fig. S43 31P NMR spectrum of rac-2a in toluene-d8.