Electronic Supporting Information for

Can chiral P(III) coordinate Eu(III)? Unexpected solvent dependent circularly polarised luminescence of BINAP and Eu(III)(hfa)3 in chloroform and acetone

Yuki Kono,a Kazuki Nakabayashi,a Sayaka Kitamura,a Motohiro Shizuma,b Michiya Fujikic*

and Yoshitane Imaia*

a Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University, 3-4-1 Kowakae, Higashi-Osaka, Osaka 577-8502, Japan.; E-mail: (Y.I.) y-imai@apch.kindai.ac.jp. b Department of Biochemistry, Osaka Municipal Technical Research Institute, 1-6-50 Morinomiya, Joto-ku, Osaka 536-8553, Japan.c Graduate School of Materials Science, Nara Institute of Science and Technology, Takayama, Ikoma, Nara 630-0192, Japan. (M.F.) fujikim@ms.naist.jp.

S1

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016

Table of Contents

Fig. S1 Normalized CPL and PL spectra of (R)-BINAP:Eu(hfa)3 = 1:1 in EtOH-free chloroform S3

Fig. S2 Normalized CPL and PL spectra of (R)-BINAP:Eu(hfa)3 in EtOH-free chloroform S4

Fig. S3 Normalized CD and UV-vis spectra of (R)- and (S)-BINAP:Eu(hfa)3 in

EtOH-free chloroform S5

Fig. S4 Negative-mode LCMS-IT-TOF spectrum of (R)-BINAP-Eu(III) S6

Fig. S5 Positive-mode LCMS-IT-TOF spectrum of (R)-BINAP-Eu(III) S7

Fig. S6 Negative-mode electrospray MS spectrum of (R)-BINAP-Eu(III) by adding NaOTf S8

Fig. S7 Positive-mode electrospray MS spectrum of (R)-BINAP-Eu(III) with NaOTf S9

Fig. S8 1H-NMR spectrum of (R)-BINAP with Eu(hfa)3 (1:1) in CDCl3 S10

Fig. S9 1H-NMR spectrum of (R)-BINAP with Eu(hfa)3 (1:1) in acetone-d6 S11

Fig. S10 1H-NMR spectrum of (R)-BINAPO with Eu(hfa)3 (1:1) in CDCl3 S12

Fig. S11 1H-NMR spectrum of (R)-BINAPO with Eu(hfa)3 (1:1) in acetone-d6 S13

Fig. S12 31P-NMR spectrum of (R)-BINAP with Eu(hfa)3 (1:1) in CDCl3 S14

Fig. S13 31P-NMR spectrum of (R)-BINAP in CDCl3

S14

Fig. S14 31P-NMR spectrum of (R)-BINAPO with Eu(hfa)3 (1:1) in CDCl3 S15

Fig. S15 31P-NMR spectrum of (R)-BINAPO in CDCl3 S15

Fig. S16 19F-NMR spectrum of hfa in CDCl3 S16

Fig. S17 19F-NMR spectrum of Eu(hfa)3 in CDCl3 S16

Fig. S18 19F-NMR spectra of (R)-BINAP and Eu(hfa)3 (1:1) in CDCl3 S17

Fig. S19 19F-NMR spectra of (R)-BINAPO and Eu(hfa)3 (1:1) in CDCl3 S17

S2

(a) (b)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

-4

-3

-2

-1

0

1

2

500 550 600 650 700 750 I= 1

/2 •

(I L+

I R)

103

• ΔI =

I L –

I R

Wavelength / nm

(R)

Fig. S1. Normalized CPL and PL spectra of (R)-BINAP:Eu(hfa)3 = 1:1 in EtOH-free chloroform. Path length 1.0 mm. (a) [Eu(hfa)3] = 1×10–5 M. ex = 300 nm, gem = +1.6 × 10–2 (593 nm), –0.95 × 10–3 (618nm). (b) [Eu(hfa)3] = 1×10–4 M. ex = 300 nm, gem = +1.4 × 10–2 (592 nm), –0.92 × 10–3 (613 nm).

S3

(a) (b)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

-2

-1

0

1

500 550 600 650 700 750 I= 1

/2 •

(I L+

I R)

103

• ΔI =

I L –

I R

Wavelength / nm

(R)

(S)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

-4

-3

-2

-1

0

1

2

500 550 600 650 700 750 I= 1

/2 •

(I L+

I R)

103

• ΔI =

I L –

I R

Wavelength / nm

(R)

(S)

(c) (d)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

-4

-3

-2

-1

0

1

2

500 550 600 650 700 750 I= 1

/2 •

(I L+

I R)

103

• ΔI =

I L –

I R

Wavelength / nm

(R)

Fig. S2. Normalized CPL and PL spectra of (R)-BINAP:Eu(hfa)3 in EtOH-free chloroform, [Eu(hfa)3] = 5 × 10–4 M (path length 1.0 mm). (a) (R)- (and (S))-BINAP:Eu(hfa)3 = 1:2, ex = 325 nm, gem for (R) = +0.89×10–2 (592 nm), –0.75×10–3 (617 nm), gem for (S) = –0.89×10–2 (592 nm), +0.75 × 10–3 (617 nm). (b) (R)- (and (S))-BINAP:Eu(hfa)3 = 2:1, ex = 325 nm, gem for (R) = +1.3 × 10–2 (592 nm), –1.15 × 10–3 (615 nm), gem for (S) = –1.3 × 10–2 (592 nm), +0.85 × 10–3 (615 nm). (c) (R)-BINAP:Eu(hfa)3 = 5:1, ex = 335 nm, gem = +1.0 × 10–2 (592 nm), –1.6 × 10–3 (618 nm). (d) (R)-BINAP:Eu(hfa)3 = 10:1, ex = 335 nm, gem = +1.1×10–2 (592 nm), –1.1×10–3 (613 nm).

S4

(a) (b)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

-20

-15

-10

-5

0

5

10

245 300 355 410 465 ε=

1/2

• (ε L

+ ε

R) /

104

M-1

cm-1

Δε=

ε L –

ε R/ M

-1 c

m-1

Wavelength / nm

(R)

(S)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

-20

-15

-10

-5

0

5

10

200 250 300 350 400 450 500 ε=

1/2

• (ε L

+ ε

R) /

104

M-1

cm-1

Δε=

ε L –

ε R/ M

-1 c

m-1

Wavelength / nm

(R)

(S)

(c) (d)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

-20

-15

-10

-5

0

5

10

245 300 355 410 465 ε=

1/2

• (ε L

+ ε

R) /

104

M-1

cm-1

Δε=

ε L –

ε R/ M

-1 c

m-1

Wavelength / nm

(R)

(S)

(e)

Fig. S3. Normalized CD and UV-vis spectra of (R)- and (S)-BINAP:Eu(hfa)3 in EtOH-free chloroform. [Eu(hfa)3] = 5 × 10–4 M (path length 1.0 mm). (a) (R)- and (S)-BINAP:Eu(hfa)3 = 1:2, |gabs| = 2.6 × 10–4 at 336 nm. (b) (R)- and (S)-BINAP: Eu(hfa)3 = 1:1, |gabs| = 5.8 × 10–4 at 336 nm. (c) (R)- and (S)-BINAP:Eu(hfa)3 = 2:1, |gabs| = 7.4 × 10–4 at 336 nm. (d) (R)-BINAP:Eu(hfa)3 = 5:1, gabs = +9.0 × 10–4 at 335 nm. (e) (R)-BINAP:Eu(hfa)3 = 10:1, gabs = +9.4 × 10–4 at 335 nm.

S5

Negative mode (full range)

100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 m/z0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

Inten.(x100,000)

206.9783

980.8188(1)

436.9408

660.8902(1)

m/z= 206.99: hfa, m/z= 660.89: BINAP, m/z= 980.82: BINAP+Eu+hfa

Negative mode (zoom-in)

977.0 978.0 979.0 980.0 981.0 982.0 983.0 984.0 985.0 986.0 m/z0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0Inten.(x100,000)

980.8188(1)

978.8171(1)

m/z = 978.82: 151Eu+BINAP+HFA, m/z= 980.82: 153Eu+BINAP+HFA

Fig. S4. Negative-mode LCMS-IT-TOF spectra of (R)-BINAP-Eu(III). Top; full spectrum. Bottom; its zoom-in spectrum.

S6

Positive mode (full)

100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 m/z0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

Inten.(x100,000)

437.1292(1)

623.1809(1)

318.9955

677.1485(1)

Positive mode (zoom-in)

934.5 935.0 935.5 936.0 936.5 937.0 937.5 938.0 938.5 939.0 939.5 940.0 940.5 941.0 941.5 m/z0.0

2.5

5.0

7.5

Inten.(x1,000)

Fig. S5. Positive-mode LCMS-IT-TOF spectra of (R)-BINAP-Eu(III). Top; full spectrum. Bottom; its zoom-in spectrum.

S7

Negative mode (full)

250 500 750 1000 1250 1500 1750 m/z0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

Inten.(x100,000)

112.9860

582.8913(1)

226.9742

488.8879(1)

394.8876

Negative mode (zoom-in)

672.5 675.0 677.5 680.0 682.5 685.0 687.5 m/z0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0Inten.(x100,000)

676.8913(1)

678.8924(1)

Fig. S6. Negative-mode electrospray MS spectrum of (R)-BINAP-Eu(III) by adding Na triflate. Two Eu(III) isotopic species with a natural abundance around m/z= 676.89 and 678.89 were observed. However, no distinct parent peaks of Eu(III)(hfa)3-BINAP (m/z= 1396.08 and 1398.08) with Na+ (m/z = 22.99) triflate (m/z = 148.95) without H2O (m/z = 18.01) and two or three H2O molecules as adducts were detected.

S8

Positive mode (full)

250 500 750 1000 1250 1500 1750 m/z0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0Inten.(x1,000,000)

655.1904(1)

Fig. S7. Positive-mode electrospray MS spectrum of (R)-BINAP-Eu(III) with NaOTf. Any Eu(III) isotopic species with natural abundance around m/z= 670 and 980 were not observed. No distinct parent peaks of Eu(III)(hfa)3-BINAP (m/z= 1396.08 and 1398.08) with Na+ (m/z = 22.99) triflate (m/z = 148.95) without H2O (m/z = 18.01) and two/three H2O molecules as adducts were detected.

S9

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

X : parts per Million : Proton

12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

891

7.

878

7.

833

7.

822

7.

446

7.

436

7.

344

7.

260

7.

150

7.

106

7.

059

6.

908

6.

831

1.

704

0.

000

35.0

0

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

X : parts per Million : Proton

8.6 8.5 8.4 8.3 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 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9

7.

891

7.

878

7.

833

7.

822

7.

446

7.

436

7.

344

7.

260

7.

150

7.

106

7.

059

6.

908

6.

831

35.0

0

Fig. S8. 1H-NMR spectra of (R)-BINAP with Eu(hfa)3 (1:1) in CDCl3.1H-NMR signals at 7.260 ppm and 1.574 ppm are due to residual CHCl3 and H2O.

S10

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

X : parts per Million : Proton

12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

984

7.

970

7.

913

7.

899

7.

226

7.

221

7.

212

7.

168

6.

769

6.

754

3.

824

3.

591

3.

354

3.

025

2.

995

2.

544

2.

040

2.

037

2.

033

2.

030

1.

264

1.

158

1.

123

1.

017

0.

891

0.

105

-0.

027

35.0

0

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

X : parts per Million : Proton

8.5 8.4 8.3 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 6.8 6.7 6.6 6.5 6.4 6.3 6.2

7.

984

7.

970

7.

913

7.

899

7.

415

7.

411

7.

401

7.

396

7.

388

7.

377

7.

363

7.

226

7.

221

7.

218

7.

212

7.

180

7.

168

7.

096

7.

094

7.

038

6.

954

6.

945

6.

943

6.

930

6.

769

6.

754

35.0

0

Fig. S9. 1H-NMR spectra of (R)-BINAP with Eu(hfa)3 (1:1) in acetone-d6.

S11

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

X : parts per Million : Proton

12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

8.

585

8.

231

8.

116

7.

983

7.

834

7.

589

7.

391

7.

263

7.

148

7.

075

6.

873

6.

568

6.

370

6.

158

6.

059

2.

171

2.

104

1.

851

0.

000

35.0

0

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

X : parts per Million : Proton

9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 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 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3

8.

585

8.

231

8.

116

7.

983

7.

834

7.

589

7.

391

7.

263

7.

148

7.

075

6.

873

6.

568

6.

370

6.

158

6.

059

35.0

0

Fig. S10. 1H-NMR spectra of (R)-BINAPO with Eu(hfa)3 (1:1) in CDCl3.

S12

abun

danc

e0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.1

0.11

X : parts per Million : Proton

12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

8.

787

8.

776

8.

292

8.

278

7.

978

7.

660

7.

402

7.

390

7.

207

7.

007

6.

654

6.

640

6.

237

3.

822

3.

272

2.

924

2.

893

2.

545

2.

043

2.

040

2.

037

2.

033

1.

269

1.

163

0.

897

-0.

023

35.0

0

abun

danc

e0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.1

0.11

X : parts per Million : Proton

9.3 9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 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 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3

8.

787

8.

776

8.

292

8.

278

7.

978

7.

964

7.

775

7.

672

7.

660

7.

648

7.

518

7.

449

7.

402

7.

390

7.

207

7.

149

7.

136

7.

124

7.

007

6.

995

6.

816

6.

761

6.

654

6.

640

6.

608

6.

237

35.0

0

Fig. S11. 1H-NMR spectra of (R)-BINAPO with Eu(hfa)3 (1:1) in acetone-d6.

S13

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

X : parts per Million : Phosphorus31

300.0 200.0 100.0 0 -100.0 -200.0 -300.0

-15.

052

Fig. S12. 31P-NMR spectrum of (R)-BINAP with Eu(hfa)3 (1:1 in molar ratio) in CDCl3.31P resonances at -15.052 ppm using a reference 31P peak (at 140 ppm) of P(OMe)3 in MeOD.

abun

danc

e0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

11.0

12.0

13.0

14.0

X : parts per Million : Phosphorus31

300.0 200.0 100.0 0 -100.0 -200.0 -300.0

-14.

862

Fig. S13. 31P-NMR spectrum of (R)-BINAP in CDCl3. 31P resonances at –14.862 ppm. 500-1000 acquisitions. Sample (5–10 mg) was dissolved in 0.6 mL of CDCl3,

corresponding to (0.6–1.2) x 10–2 M.

S14

abun

danc

e 00.

10.

20.

30.

40.

5

X : parts per Million : Phosphorus31

110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0 -10.0 -20.0 -30.0 -40.0 -50.0 -60.0 -70.0 -80.0 -90.0 -100.0 -110.0

28.

885

-65.

702

-69.

167

Fig. S14. 31P-NMR spectrum of (R)-BINAPO with Eu(hfa)3 (1:1 in molar ratio) in CDCl3.Major 31P signal at -69.167 infers the coordination of P(V)=O of BINAPO, whilst minor 31P signal at +28.885 ppm is non-coordinated P(V)=O of　BINAPO. The origin of minor 31P-

NMR signal at -65.702 ppm is unclear. 500–1000 acquisitions. Sample (5-10 mg) was dissolved in 0.6 mL of CDCl3, corresponding to (0.6–1.2) x 10–2 M.

abun

danc

e0

1.0

2.0

3.0

X : parts per Million : Phosphorus31

300.0 200.0 100.0 0 -100.0 -200.0 -300.0

28.

912

Fig. S15. 31P-NMR spectrum of (R)-BINAPO in CDCl3. 31P resonances at +28.912 ppm.

S15

abun

danc

e0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.

011

0.0

120.

0

X : parts per Million : Fluorine19

50.0 40.0 30.0 20.0 10.0 0 -10.0 -20.0 -30.0 -40.0 -50.0 -60.0 -70.0 -80.0 -90.0 -100.0 -110.0 -120.0 -130.0 -140.0 -150.0 -160.0 -170.0 -180.0 -190.0

-76.

500

Fig. S16. 19F-NMR spectrum of hfa in CDCl3. 19F resonances at −76.500 ppm.

abun

danc

e-0

.02-0

.01

00.

010.

020.

030.

040.

050.

060.

070.

080.

090.

10.

110.

120.

130.

140.

150.

160.

17

X : parts per Million : Fluorine19

50.0 40.0 30.0 20.0 10.0 0 -10.0 -20.0 -30.0 -40.0 -50.0 -60.0 -70.0 -80.0 -90.0 -100.0 -110.0 -120.0 -130.0 -140.0 -150.0 -160.0 -170.0 -180.0 -190.0

-79.

059

Fig. S17. 19F-NMR spectrum of Eu(hfa)3 in CDCl3. 19F resonances at −79.059 ppm.

S16

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

X : parts per Million : Fluorine19

50.0 40.0 30.0 20.0 10.0 0 -10.0 -20.0 -30.0 -40.0 -50.0 -60.0 -70.0 -80.0 -90.0 -100.0 -110.0 -120.0 -130.0 -140.0 -150.0 -160.0 -170.0 -180.0 -190.0

-79.

069

-80.

057

Fig. S18. 19F-NMR spectrum of (R)-BINAP and Eu(hfa)3 ( = 1:1 in molar ratio) in CDCl3.19F resonances at −79.099 ppm (major) and −80.057 ppm (minor).

abun

danc

e0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10.0

11.0

X : parts per Million : Fluorine19

50.0 40.0 30.0 20.0 10.0 0 -10.0 -20.0 -30.0 -40.0 -50.0 -60.0 -70.0 -80.0 -90.0 -100.0 -110.0 -120.0 -130.0 -140.0 -150.0 -160.0 -170.0 -180.0 -190.0

-78.

009

-78.

549

Fig. S19. 19F-NMR spectrum of (R)-BINAPO and Eu(hfa)3 ( = 1:1 in molar ratio) in CDCl3. 19F resonances at −78.099 ppm (minor) and −78.549 ppm (major).

S17