supporting information singlet and triplet energy transfer rate

1

Supporting Information

Singlet and Triplet Energy Transfer Rate Acceleration by Additions of

Clusters in Supramolecular Pigment-Organometallic Cluster Assemblies†

Bin Du,a,b Christine Stern,b Pierre D. Harveya,b* aDépartement de Chimie, Université de Sherbrooke, 2550 Boulevard de l’Université, Sherbrooke,

Quebec, Canada J1K 2R1, Fax: 001-819-821-8017. Tel: 001-819-821-7092. E-mail:

[email protected]

bInstitut de Chimie Moléculaire de l’Université de Bourgogne (ICMUB,UMR 5260), Université de

Bourgogne, Dijon, France.

Materials.

The [Pd3(dppm)3(CO)]2+ PF6 cluster1, 5-(4-carboxyphenyl)-10,15,20-tritolyporphyrinatozinc (4),

5,15-2-(4-carboxyphenyl)-10,20-ditolyporphyrinatozinc (5) and 5,10,15, 20-4-(4-carboxyphenyl)-

tetratolyporphyrinatozinc (6) were synthesized according to the previous literature3. Carboylate salts

MCO2ZnP (I), DCO2ZnP (II) and TCO2ZnP (III) were synthesized by ion-exchange resin4.

Figure S1. The synthetic routes of carboxylate-porphyrin salts

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2011

2

General Procedure for the Synthesis of Porphyrin Salts, with the synthesis of DCO2ZnP (II) as

an example. The porphyrin dicarboxylic acid (5, 0.05 mmol) was dissolved in methanol (20 mL). The

solution was passed through DOWEX HCRW2 (Na form) ion-exchange resin. As the methanol and

water were removed, the porphyrin salt was obtained as purple solid. Yield: 60 %. 1H NMR (DMSO, δ,

ppm): 8.19 (m, 8H), 8.25-8.22 (m, 4H), 8.08-8.03 (m, 8H), 87.62-7.59 (m, 4H), 2.68 (s, 6H).

Elemental analysis (%) calcd for C48H30N4Na2O4Zn+4H2O: C, 63.34; H, 4.21; N, 6.16; Found: C, 63.87;

H, 4.53; N, 5.78.

Figure S2. Models of [Pd3(dppm)3(CO)]2+ with carboxylate-porphyrins showing the cavity above the

unsaturated face of the Pd3 center. Up, ball-and-stick model for MCO2ZnP-(Pd32+); bottom, space filling

model for DCO2ZnP-(Pd32+)2.


3

Spectroscopic Measurements.

The spectroscopic and photophysical measurements were carried out in methanol and the mixture of

methanol and 2-MeTHF, which was distilled with calcium hydride under argon. The absorption

measurements of the [Pd3(dppm)3(CO)]2+ cluster, associated with the binding constant calculation, were

carried out in methanol because the largest difference can be shown in λmax between the free cluster and

host-guest assembly.

Methodology.

The binding constants (K1n : K11, K12, and K14) were measured according to the typical method as follows:

Two different solutions (A and B) were prepared in methanol. Solution A contained the “free cavity”

cluster [Pd3(dppm)3(CO)]2+ (PF6-)2. Solution B was the mixture of the cluster, which contains exactly the

same concentration as that used in solution A, with the porphyrin carboxylate salt. The spectroscopic

changes induced by solution A as a result of additions of constant volume (0.1 mL) of solution B were

monitored by measuring the absorption spectra after each addition. The competitive binding constants

(K11, K12, and K14) were measured by plotting 1/ΔA vs 1/[substrate] (Benesi-Hildebrand), where ΔA is

the absorbance change upon an increase in the substrate concentration. The substrate concentration was

corrected based on the change of the total volume at each addition, and these adjusted values were used

for the plots. The ratio of intercept/slope in this plot gives K11, K12, and K14. The binding constant values

were more accurately evaluated by using the Scatchard and Scott plots ΔA/[substrate] vs -ΔA with K1n=

-slope (Scatchard) and -[substrate]/ΔA vs [substrate] with K1n= slope/intercept (Scott) with the

experimental uncertainties 10%. The uncertainties are based on multiple measurements. The Scott and

Scatchard’s plots are presented in this ESI.

The measurement to identify the formation of 1:2 and 1:4 assembiles was carried out in the

following way. Two different solutions (C and D) were prepared in methanol. Solution C contained the

free carboxylate-porphyrins. Solution D was the mixture of the porphyrin, which contains exactly the

same concentration as that used in solution C, with the cluster. The uncertainties (10%) are based on

multiple measurements.


4

Instruments

UV-visible spectra were recorded on a Varian Cary 300 spectrophotometer. The emission spectra were

obtained using a double-monochromator Fluorolog 2 instrument from Spex. The emission lifetimes were

measured on a TimeMaster model TM-3/2003 apparatus from PTI. The source was a nitrogen laser with

a high-resolution dye laser (fwhm ~ 1400 ps), and the fluorescence lifetimes were obtained from

deconvolution or distribution lifetime analysis. The uncertainties were about 50-100 ps. The

phosphorescence lifetimes were performed on a PTI LS-100 using a 1 μs tungsten flash lamp (fwhm ~1

μs). The flash photolysis spectra and the transient lifetimes were measured with a Luzchem spectrometer

using the 355 nm line of a YAG laser from Continuum (Serulite) and the 530 nm line from a OPO

module pump by the same laser (fwhm =3 ns).

0

0.2

0.4

0.6

0.8

1

1.2

350 400 450 500 550 600 650

DCO2Zn

TCO2Zn

Nor

mal

ized

Inte

nsity

Wavelength (nm)

Figure S3. Absorption spectrum of DCO2ZnP and TCO2ZnP in MeOH at 298K.


5

0

0.2

0.4

0.6

0.8

1

600 650 700 750 800 850

DCO2ZnP

TCO2ZnP

Nor

mal

ized

Inte

nsity

Wavelength (nm) Figure S4. The corrected emission of DCO2ZnP-(Pd3

2+)2 and TCO2ZnP-(Pd32+)4 at 298 K in

2MeTHF:MeOH (20:1) mixture . λexc = 560nm.

0

0.2

0.4

0.6

0.8

1

600 650 700 750 800

DCO2ZnP

TCO2ZnP

Inte

nsity

Wavelength (nm)

Figure S5. The corrected emission of DCO2ZnP-(Pd32+)2 and TCO2ZnP-(Pd3

2+)4 at 298 K in

2MeTHF:MeOH (20:1) mixture . λexc = 560nm.


6

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

400 500 600 700 800 900

8-17.6 (10-6s)25.6-33.6 (10-6s)

41.6-51.2 (10-6s)61-652 (10-6s)

Inte

nsity

Wavelength (nm)

Figure S6. Transient absorption spectrum of MCO2ZnP in MeOH at 298K. λexc = 355 nm. The delay

times between the pump and probe pulses are placed in the figure.

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

400 500 600 700 800 900

3.0-7.2 (10-6s)

12-14 (10-6s)18.2-20.7 (10-6s)31.3-324 (10-6s)

Inte

nsity

Wavelength (nm)

Figure S7. Transient absorption spectrum of MCO2ZnP-(Pd32+) in MeOH at 298K. λexc = 355 nm. The

delay times between the pump and probe pulses are placed in the figure.


7

0

0.02

0.04

0.06

0.08

0.1

0.12

500 600 700 800 900

25.6-51.2 (10-6s)

76-108 (10-6s)153-185 (10-6s)243-3275 (10-6s)

Inte

nsity

Wavelength (nm)

Figure S8.Transient spectrum of DCO2ZnP in MeOH at 298K. λexc = 355 nm. The delay times between

the pump and probe pulses are placed in the figure.

0

0.02

0.04

0.06

0.08

0.1

400 500 600 700 800 900

0.64-1.28 (10-6s)

1.92-2.56 (10-6s)3.68-4.48 (10-6s)

5.44-52.51 (10-6s)

Inte

nsity

Wavelength (nm) Figure S9. Transient absorption spectrum of DCO2ZnP-(Pd3

2+)2 in MeOH at 298K. λexc = 355 nm. The



8

0

0.05

0.1

0.15

0.2

0.25

0.3

400 500 600 700 800 900

44-83 (10-6s)

121-134 (10-6s)166-192 (10-6s)243-3257 (10-6s)

Inte

nsity

Wavelength (nm) Figure S10. Transient absorption spectrum of TCO2ZnP (alone) in MeOH at 298K. λexc = 355 nm. The


0

0.5

1

1.5

400 450 500 550 600 650 700

D-free cavityFHJLNPRTVXZ

Inte

nsity

Wavelength (nm)

D

F

Z

Figure S11. UV-vis spectra for the addition of MCO2ZnP into a MeOH solution of

[Pd3(dppm)3(CO)3](PF6)2 = 6.7 × 10-5 M. Curve F-Z obtained with successive addition of 6.7 × 10-9 M

of MCO2ZnP with 0.1ml for every addition. (The arrows indicate the direction of absorption change with

change in concentration).


9

0

0.2

0.4

0.6

0.8

1

1.2

1.4

400 450 500 550 600 650 700

B-free cavityDFHJLNPRTVXZAB

Inte

nsity

Wavelength (nm)

BAB

Figure S12. UV-vis spectra for the addition of DCO2ZnP (3.35 × 10-5M) into a MeOH solution of

[Pd3(dppm)3(CO)3](PF6)2 (6.7 × 10-5M) with 0.1ml for every addition. Curves D-AB obtained with

successive additions of 3.35 × 10-9 M of DCO2ZnP.

7 10-5

7.5 10-5

8 10-5

8.5 10-5

9 10-5

9.5 10-5

0 2 10-6 4 10-6 6 10-6 8 10-6 1 10-51.2 10-51.4 10-5

y = 7.4051e-05 + 1.6035x R= 0.8471

[sal

t]/A(

mol

/L/A

bsor

b.)

[salt] mol/L K12 21654 M-1


10

1.05 104

1.1 104

1.15 104

1.2 104

1.25 104

1.3 104

1.35 104

1.4 104

0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16

Scatchhard ploty = 13469 - 20877x R= 0.8091

A/[s

alt](

abso

b./m

ol/L

)

A (Absorb.)

K12 20877 M-1

Figure S13. Scott plots and Scatchard for the 2:1 formation of DCO2ZnP-(Pd32+)2 assembly at 298 K in

MeOH (20:1) mixture.

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

400 450 500 550 600 650 700

Free cavityFJNDHLPRIn

tens

ity

Wavelength (nm) Figure S14. UV-vis spectra for the addition of DCO2ZnP into a MeOH solution of

[Pd3(dppm)3(CO)3](PF6)2 (3.35 × 10-5 M). Curves D-R obtained with successive additions of

3.35×10-5 M of DCO2ZnP with 0.1ml for every addition. (The arrows indicate the direction of

absorption change with change in concentration).


11

0

0.2

0.4

0.6

0.8

1

1.2

1.4

450 500 550 600

B-free cavity

DFHJLNPRTV

Inte

nsity

Wavelength (nm)

B

J

、

Figure S15. Uv-visible spectra for the addition of TCO2ZnP into a MeOH solution of

[Pd3(dppm)3(CO)3](PF6)2 (6.7 × 10-5 M). Curves D-V obtained with successive addition of 1.68×10-5 M

of TCO2ZnP with 0.1 ml for every addition. (The arrows indicate the direction of absorption change with

change in concentration).


12

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

350 400 450 500 550 600 650

aloneDFHJLNPRTVXZAB

Inte

nsity

W ave length (nm )

D

A B

465

470

475

480

485

490

495

500

0 1 2 3 4 5

Wav

elen

gth

(nm

)

[Pd3]/[DCOOZnP]

Figure S16. Top: UV-vis spectra for the addition of [Pd3(dppm)3(CO)3](PF6)2 into a MeOH solution of DCO2ZnP (0.75 × 10-5 M). Curves D-AB obtained with successive additions of 6.7×10-5 M of [Pd3(dppm)3(CO)3](PF6)2. Bottom: Absorption shifts of [Pd3(dppm)3(CO)3](PF6)2 in MeOH as a function of the ratio of added cluster to the DCO2ZnP –containing solution.


13

6 10-5

6.5 10-5

7 10-5

7.5 10-5

8 10-5

8.5 10-5

9 10-5

1 10-62 10-63 10-64 10-65 10-66 10-67 10-68 10-69 10-6

Scott Plot

y = 8.1254e-05 - 2.0841x R= 0.80135

[sal

t]/A(

mol

/L/A

bsor

b.)

[salt] mol/L

K14 25729 M-1

1.2 104

1.25 104

1.3 104

1.35 104

1.4 104

1.45 104

1.5 104

1.55 104

1.6 104

0 0.02 0.04 0.06 0.08 0.1 0.12 0.14

Scathhard PlotY = 12247 + 28988X

R= 0.75379

A/[s

alt](

abso

b./m

ol/L

)

A (Absorb.) K14 28998 M-1

Figure S17. Scott plots and Scatchard, for the formation of TCO2ZnP-(Pd32+)4.


14

0

5 104

1 105

1.5 105

2 105

550 600 650 700 750 800

1:2 AssemblyDCOOZnP-Alone

Inte

nsity

Wavelength (nm) Figure S18. The emission of DCO2ZnP and DCO2ZnP-(Pd3

2+)2 at 298 K in MeOH. λexc = 560nm (the

concentration of DCO2ZnP is the same with the concentration of DCO2ZnP-(Pd32+)2).

Figure S19. The emission of DCO2ZnP and DCO2ZnP-(Pd32+)2 at 77 K in MeOH. λexc = 560nm (the

concentration of DCO2ZnP is the same with the concentration of DCO2ZnP-(Pd32+)2).


15

Table S1. K1n Values for MCO2ZnP , DCO2ZnP, and TCO2ZnP

with [Pd3(dppm)3(CO)]2+ in MeOH at 298 K.a

Substrate K1n( M-1) Scott Scatchard

MCO2ZnP-(Pd32+) b K11 19300 19000

DCO2ZnP-(Pd32+)2 K12 21700 20900

TCO2ZnP-(Pd32+)4 K14 25700 29000

a The uncertainties are ~10% based on multiple measurements. b Ref. 2.

References:

1 (a) G. Ferguson, B. R. Lloyd, and R. Puddephatt, Organometallics, 1986, 344. (b) L.

Manojlovic-Muir, K. W. Muir, B. R. Lloyd and R. J. Puddephatt, J. Chem. Soc., Chem. Commun.,

1983, 1336.

2 S. M. Aly, C. Ayed, C. Stern, R. Guilard, Alaa S. Abd-El-Aziz, and P.D. Harvey, Inorg. Chem.,

2008, 47, 21.

3 (a) E. Galoppini, J. Rochford, H. Chen, G. Saraf, Y. Lu, A. Hagfeldt, and G. Boschloo, J. Phys.

Chem. B., 2006, 110, 16159; (b) J. Rochford, D. Chu, A. Hagfeldt, and E. Galoppini, J. Am. Chem.

Soc., 2007, 129, 4655; (c) J. Rochford, and E. Galoppini, Langmuir, 2008, 24, 5366.

4 J. Rochford, D. Chu, A. Hagfeldt, and E. Galoppini, J. Am. Chem. Soc., 2007, 129, 4655.

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