ruthenium-cobalt dinuclear complexes as photocatalysts for ... · ruthenium-cobalt dinuclear...

Ruthenium-Cobalt Dinuclear complexes as Photocatalysts for CO2 reduction

X.Wang,a V. Goudy,b G. Genesiob, J. Maynadiéb, D. Meyerb and M. Fontecavea*

aLaboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Collège de France, Université P. et M. curie, PSL research University, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, FranceE-mail: [email protected]

bLaboratoire des Systèmes Hybrides pour la Séparation, Institut de Chimie Séparative de Marcoule, UMR 5257 CEA/CNRS/UM/ENSCM, BP17171, 30207 Bagnols-sur-Cèze CEDEX, France

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2017

mailto:[email protected]

Index

A. Synthesis and characterization of [Ru(bpy-Me2)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 and complexes 1-5 3

Mass Spectra (Figures S1-S6) 5

UV-visible spectra (Figures S7-S9) 11

Emission Spectra (Figures S10-S15) 14

Lifetime decay profile (Figures S16-S21) 17

Cyclic Voltammograms (Figures S22-S27) 20

B. Photocatalytic studies 23

Catalytic essay (Figures S28-S30) 24

2

A. Synthesis and characterization of [Ru(bpy-Me2)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 and complexes 1-5

A.1 Materials. Reagent grade chemicals and solvent obtained from commercial source were used as received. 1,10-phenanthroline-5,6-dione1 and cis-[Ru(bpy)2Cl2]2 were synthetized according to the literature procedures. cis-[Ru(bpy-Me2)2Cl2] was prepared from a modified reported method using 5,5’-dimethyl-2,2’-bipyridine instead of 2,2’-bipyridine.3 2-(3-formylphenyl)imidazo[4,5-f]-[1,10]phenanthroline, [Ru(bpy)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2, Ru(bpy)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)4-tert-butylphenol)](PF6)2 and complex 6 were synthetized as previously described.4

A.2 Materials characterisation. Elemental (C, H and N) analyses were performed on a flash EA 1112 (ThermoFinnigan 2003) instrument. Elemental (Ru and Co) analyses were determined by ICP-AES on a Perkin Elmer Optima 2000 DV after full digestion of complexes in a 2M HNO3 solution. 1H NMR were recorded on a Bruker AvanceIII 400 spectrometer with (CD3)2SO as solvent at room temperature. Electro-spray mass spectra were obtained in acetonitrile at room temperature with an Alliance 2790 Waters analyser with (CH3)2SO as mobile phase. UV-visible spectra were measured on a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer in acetonitrile at room temperature. Cyclic voltammetry was performed on a biologic SP 300 potensiostat. The supporting electrolyte was tetrabutylammonium hexafluorophosphate in dry and deaerated acetonitrile by purging with nitrogen. A standard three electrodes system was used with a glassy carbon working electrode, platinum counter-electrode and a nonaqueous Ag/AgCl reference electrode. Emission spectra and luminescence lifetime were recorded with a Horiba FluoroMax-4 in deaerated acetonitrile at room temperature. The luminescence lifetime were calculated with the Time Correlated Single Photon Counting method.

A.3 Synthesis of [Ru(bpy-Me2)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2.

A mixture of 2-(3-formylphenyl)imidazo[4,5-f]-[1,10]phenanthroline (0.080 g, 0.28 mmol, 1.2 equiv), Ru(bpy-Me2)2(phendione)Cl2 (0.172 g, 0.22 mmol, 1 equiv) and ammonium acetate (0.351 g, 4.56 mmol, 20 equiv) in acetic acid (5 mL) was refluxed for 16 hours and then cooled to room temperature. Addition of NH4PF6 gave a brown precipitate which was collected and then washed with water, and ethanol/ether. (0.216 g, 74%)

Elemental analysis: calculated for C56H46N12P2F12Ru: C 52.63%, H 3.63%, N 13.15%; Found: C 52.32%, H 3.47%, N 13.38%1H NMR (400 MHz, ppm, DMSO-d6): δ 14.60 (s, 1H), 14.16 (s, 1H), 9.32 (s, 1H), 9.14-9.09(m, 8H), 8.76 (s, 2H), 8.72 (s, 2H), 8.47-8.40 (m, 2H), 8.11 (d, J = 5.2 Hz, 2H), 8.01-7.88 (m, 5H), 7.68 (d, J = 5.6 Hz, 2H), 7.44 (m, 4H), 7.19 (d, J = 5.4 Hz, 2H), 2.57 (s, 6H), 2.47 (s, 6H).

ESI-MS (DMSO, m/z): 492.14 (M2+/2, [C56H42N12Ru]2+/2 requires 492.14)

A.4 Synthesis of the ruthenium-cobalt dinuclear complexes

Complex 1. A mixture of [Ru(bpy)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 (0.100 g, 0.08 mmol, 1 equiv) and Co(Phen)2Cl2 (0.053 g, 0.11 mmol, 1.3 equiv) in methanol (3 mL) was

3

refluxed for 12 hours and then cooled to room temperature. Methanol was eliminated under vacuum and the solid was washed with water, and ethanol/ether. (0.098 g, 72%)

Elemental analysis: calculated for C76H50N16P2F12Cl2RuCo: C 53.44%, H 2.95%, N 13.12%; Found: C 53.13%, H 2.82%, N 13.30%

ICP-AES (HNO3 2M / [1] = 84 mg L-1): calculated Ru 5.92%, Co 3.45%; Found Ru 5.87%, Co 3.43%

ESI-MS (DMSO, m/z): 448.76 (M3+/3, [C76H49N16RuCo]3+/3 requires 448.77)

Complex 2. The same procedure as for 1 was used with [Ru(bpy)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 (0.097 g, 0.08 mmol, 1 equiv) and Co(terpy)Cl2 (0.064 g, 0.10 mmol, 1.3 equiv) as starting compounds. (0.086 g, 70%)

Elemental analysis: calculated for C67H45N15P2F12Cl2RuCo: C: 50.90%, H: 2.87%, N: 13.29%; Found: C 51.22%, H 2.78%, N 13.41%



Complex 3. The same procedure as for 1 was used with [Ru(bpy-Me2)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 (0.120 g, 0.09 mmol, 1 equiv) and Co(Phen)2Cl2 (0.058 g, 0.12 mmol, 1.3 equiv) as starting compounds. (0.117 g, 75%)




Complex 4. The same procedure as for 1 was used with [Ru(bpy-Me2)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 (0.120 g, 0.09 mmol, 1 equiv) and Co(terpy)Cl2 (0.077 g, 0.12 mmol, 1.3 equiv) as starting compounds. (0.117 g, 75%)




Complex 5. The same procedure as for 1 was used with Ru(bpy)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)4-tert-butylphenol)](PF6)2 (0.071 g, 0.05 mmol, 1 equiv) and Co(Phen)2Cl2 (0.034 g, 0.07 mmol, 1.3 equiv) as starting compounds. (0.063 g, 72%)

Elemental analysis: calculated for C80H58N16OP2F12Cl2RuCo: C 53.97%, H 3.28%, N 12.59%, Found: C 54.12%, H 3.18%, N 12.87%


ESI-MS (DMSO, m/z): 472.77 (M3+/3, [C80H58N16ORuCo]3+/3 requires 472.81)

4

m/z

A.5 Mass Spectra

5

Figure S1. ESI spectrum of [Ru(bpy-Me2)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 in DMSO (m/z: 492.14= Ru-complex2+/2; 328.43= Ru-complex3+/3)

6

Figure S2. ESI spectrum of complex 1 in DMSO (m/z: 464.10= Ru-complex2+/2;

7

m/z

448.75= 13+/3; 309.74= Ru-complex3+/3; 299.57= Co(Phen)32+/2; 209.54= Co(Phen)2

2+/2; 181.08= PhenH+)

8

Figure S3. ESI spectrum of complex 2 in DMSO (m/z: 464.10= Ru-complex2+/2; 406.41= 23+/3)

9

m/z

Figure S4. ESI spectrum of complex 3 in DMSO (m/z: 500.13= Ru-complex2+/2; 472.77= 33+/3; 333.76= Ru-complex3+/3; 209.54= Co(Phen)2

2+/2; 181.08= PhenH+)

10

m/z

Figure S5. ESI spectrum of complex 4 in DMSO (m/z: 492.14= Ru-complex2+/2; 425.09= 43+/3; 328.43= Ru-complex3+/3; 262.56= Co(terpy)2

2+/2; 146.01= Co(terpy)2+/2)

11

m/z

Figure S6. ESI spectrum of complex 5 in DMSO (m/z: 500.13= Ru-complex2+/2; 472.77= 53+/3; 333.76= Ru-complex3+/3; 209.54= Co(Phen)2

2+/2; 181.08= PhenH+)

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m/z

0

0,5

1

1,5

2

2,5

3

220 320 420 520 620 720

Abso

rban

ce

Wavenumber (nm)

0

0,2

0,4

0,6

0,8

1

1,2

200 300 400 500 600 700 800

Abso

rban

ce

Wavelength (nm)

A.6 UV-visible spectra

Figure S7. UV-vis spectra of [Ru(bpy-Me2)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 (red), complex 3 (green) and complex 4 (blue) in CH3CN.

Figure S8. UV-vis spectra of [Ru(bpy)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 (green), complex 1 (red) and complex 2 (blue) in CH3CN.

13

0

0,5

1

1,5

2

2,5

200 300 400 500 600 700 800

Abso

rban

ce

Wavelength (nm)

Figure S9. UV-vis spectra of complex 5 (red) and complex 6 (blue) in CH3CN.

14

450 500 550 600 650 700 750 800 850 900-100000

0

100000

200000

300000

400000

500000

600000

700000

Inte

nsity

Wavelength (nm)

450 500 550 600 650 700 750 800 850 900

0

100000

200000

300000

400000

500000

600000

S1c

/ R1c

(CPS

/ M

icroA

mps

)

Wavelength (nm)

Inte

nsity

A.7 Emission Spectra

Figure S10. Emission spectrum of [Ru(bpy-Me2)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 in CH3CN

Figure S11. Emission spectrum of complex 1 in CH3CN

15

450 500 550 600 650 700 750 800 850 900-50000

0

50000

100000

150000

200000

250000

300000

350000

400000In

tens

ity

Wavelength (nm)

450 500 550 600 650 700 750 800 850 900

0

200000

400000

600000

800000

1000000

1200000

Inte

nsity

Wavelength (nm)



16

450 500 550 600 650 700 750 800 850 900

0

200000

400000

600000

800000In

tens

ity

Wavelength (nm)

450 500 550 600 650 700 750 800 850 900

0

100000

200000

300000

400000

Inte

nsity

Wavelength (nm)



17

A.8 Lifetime decay profile

18

1000 2000 3000 4000

0

2000

4000

6000

8000

10000C

ount

s (L

in)

Channels

15 bis

= 1418 ns

820 1640 2460 3280

Time (ns)

19

Figure S16. Lifetime decay profile of [Ru(bpy-Me2)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 in CH3CN (χ² = 1.022)

20

1000 2000 3000 4000

0

2000

4000

6000

8000

10000Co

unts

(Lin

)

Channels

13

= 767 ns

820 1640 2460 3280

Time (ns)

21

Figure S17. Lifetime decay profile of complex 1 in CH3CN (χ² = 1.053)

22

1000 2000 3000 4000

0

2000

4000

6000

8000

10000Co

unts

(Lin

)

Chanel

14

Channels

= 699 ns

820 1640 2460 3280

Time (ns)

23


24

0 1000 2000 3000 4000

0

2000

4000

6000

8000

10000Co

unts

(Lin

)

Chanel

9A

Channels

= 706 ns

820 1640 2460 3280

Time (ns)

25


26

1000 2000 3000 4000

0

2000

4000

6000

8000

10000

Coun

ts (L

in)

Channels

18

= 647 ns

820 1640 2460 3280

Time (ns)

27

1000 2000 3000 4000

0

2000

4000

6000

8000

10000

Coun

ts (L

in)

Channels

20

= 813 ns

820 1640 2460 3280

Time (ns)


28


29

-8,00E-03

-6,00E-03

-4,00E-03

-2,00E-03

0,00E+00

2,00E-03

4,00E-03

6,00E-03

8,00E-03

-3 -2,5 -2 -1,5 -1 -0,5 0 0,5 1 1,5 2 2,5

I (µA

)

Ewe/V vs Ag/AgCl nonaqueous

-1,00E-02

-5,00E-03

0,00E+00

5,00E-03

1,00E-02

-3 -2,5 -2 -1,5 -1 -0,5 0 0,5 1 1,5 2

I (µA

)


A.9 Cyclic Voltammograms

Figure S22. Cyclic voltammogram of [Ru(bpy-Me2)2(2,6-di(1H-imidazo[4,5-f][1,10]phenantrolin-2-yl)benzene)](PF6)2 in acetonitrile at 50 mV/s

Figure S23. Cyclic voltammogram of complex 1 in acetonitrile at 50 mV/s

30

-0,008

-0,006

-0,004

-0,002

0

0,002

0,004

0,006

-3 -2,5 -2 -1,5 -1 -0,5 0 0,5 1 1,5 2 2,5

I (µA

)




31

-0,007

-0,006

-0,005

-0,004

-0,003

-0,002

-0,001

0

0,001

0,002

0,003

-3 -2,5 -2 -1,5 -1 -0,5 0 0,5 1 1,5 2 2,5

I (µA

)


-0,006

-0,004

-0,002

0

0,002

0,004

0,006

-3 -2,5 -2 -1,5 -1 -0,5 0 0,5 1 1,5 2 2,5

I (µA

)




32

-8,00E-03

-6,00E-03

-4,00E-03

-2,00E-03

0,00E+00

2,00E-03

4,00E-03

6,00E-03

-3 -2,5 -2 -1,5 -1 -0,5 0 0,5 1 1,5 2 2,5

I (µA

)


B. Photocatalytic studies

B.1 Photocatalytic experimental details

Photochemical reactions were performed using a 300 W, high pressure Xe arc lamp (Oriel Instruments). The beam was passed through an infrared filter, a collimating lens, a filter holder equipped with a 415 nm band pass filter. Samples were prepared in a 1 cm path length quartz cuvette (Starna) which was placed in a temperature controlled cuvette holder (Quantum Northwest) maintained at 20°C with a circulated water bath.

For the entirety of the study, a 5:1 (v:v) mixture of ACN/TEOA was used as a solvent mixture (ACN and TEOA purchased from Sigma Aldrich and used without further purification). The electron donor utilized was a 100 mM solution of BIH (BIH was synthesized according to previously reported procedure5). For assays of complexes 1-6, 0.1 mM of each complex was utilized. For assays consisting mononuclear catalyst and [Ru(bpy)3]Cl2 photosensitizer (purchased from Strem Chemicals, used without further purification), 0.1 mM of each compound was utilized. Samples were saturated with CO2 via directely bubbling CO2 through the solution mixture for 10 minutes.

B.2 Product Detection Chemical Analysis Detection Details

H2 measurements were performed by gas chromatography on a Shimadzu GC-2014 equipped with a Quadrex column, a Thermal Conductivity Detector and using N2 as a carrier gas. CO was measured using a Shimadzu GC-2010 Plus gas chromatography, fitted with a S9 Restek Shin Carbon column, Helium carrier gas, a methanizer and a Flame Ionization Detector. The typical volume of gas injected was 50 μL.

Formate concentration was determined using a Metrohm 883 Basic IC plus ionic exchange chromatography instrument, using a Metrosep A Supp 5 column and a conductivity detector. A typical measurement requires the sampling of 200 μL of solution, followed by a 100-fold dilution in deionised 18 MΩ water and injection of 20 μL of the final solution into the instrument.

33

B.3 Catalytic essay

Figure S28. CO (dot), H2 (square) and formate (triangle) evolution catalyzed by a 0.1 mM solution of complex 5 in the presence of 100 mM BIH as electron donor in a CO2-saturated ACN/TEOA (5:1, v:v) solvent mixture upon irradiation with a 300W Xe arc lamp equipped with a 415 nm filter at 20°C

Figure S29. CO (dot), H2 (square) and formate (triangle) evolution catalyzed by a solution of 0.1 mM [Co(phen)3]Cl2 and 0.1 mM [Ru(bpy)3]Cl2 in the presence of 100 mM BIH as electron donor in a CO2-saturated ACN/TEOA (5:1, v:v) solvent mixture upon irradiation with a 300W Xe arc lamp equipped with a 415 nm filter at 20°C

34

Figure S30. CO (dot), H2 (square) and formate (triangle) evolution catalyzed by a solution of 0.1 mM Ru(bpy)2Cl2 and 0.1 mM [Ru(bpy)3]Cl2 in the presence of 100 mM BIH as electron donor in a CO2-saturated ACN/TEOA (5:1, v:v) solvent mixture upon irradiation with a 300W Xe arc lamp equipped with a 415 nm filter at 20°C

35

References

1 W. Paw and R. Eisenberg, Inorg. Chem., 1997, 36, 2287–2293.

2 C. Viala and C. Coudret, Inorganica Chim. Acta, 2006, 359, 984–989.

3 C. E. McCusker and J. K. McCusker, Inorg. Chem., 2011, 50, 1656–1669.

4 V. Goudy, J. Maynadié, X. L. Goff, D. Meyer and M. Fontecave, New J Chem, 2016, 40, 1704–1714.

5 X.-Q. Zhu, M.-T. Zhang, A. Yu, C.-H. Wang and J.-P. Cheng, J. Am. Chem. Soc., 2008, 130, 2501–2516.

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