Supplementary Material (ESI) for PCCP This journal is © the Owner Societies 2010
Spectroelectrochemical Studies of Cation Percolation on Functionalized Nanocrystalline TiO2 Films: A Comparison of Two Different Ruthenium Complexes Xiaoe Li a, Mohammad K. Nazeeruddin b, Mukundan Thelakkatc, Piers Barnes a, Ramόn Vilar a and James Durrant*a a
Department of Chemistry, Imperial College London, London SW7 2AZ, U.K. Fax: +44(0)2075945621; Tel: +44(0)20075945801; E-mail:
[email protected] b
Laboratory for Photonics and Interfaces, Institute of Molecular and Biological Chemistry, School of Basic Sciences, Swiss Federal Institute of Technology, CH-1015 Lausanne, Switzerland. c
Applied Functional Polymers, University of Bayreuth, Bayreuth, 95440, Germany.
1. Dye cation lifetime measurement Fig.S1 shows the life time measurements for HW456 dye. The potential step is from 0.4 V to +0.45 V vs Fc/Fc+.
Normalized ΔODλ=770 nm
1.0 0.8 HW456-TiO2 film +
+0.45 V vs Fc/Fc
0.6 0.4 0.2 0.0 0
10
20
30 40 Time, t (min)
50
60
70
Figure S1 Lifetime measurements for HW456 on nanocrystalline TiO2 film in non-aqueous solution (0.1 M TBAP in acetonitrile).
2. CV and CVA of N621 dye free solution
i x 10 (A)
200
Scan rate: 100 mV/s
6
100 0
ΔODλ=750 nm
0.003 0.002 0.001
dΔOD/dE (a.u/V)
0.000 0.01 0.00 x -1 -0.01 -0.4
-0.2
0.0
0.2
0.4
0.6
+
E vs Fc/Fc (V)
Figure S2 Spectroelectrochemical characterisation CV (a), CVA (b), and DCVA (c) of N621 free in solution. Arrows show the scan directions. In order to make it readily comparable to CV data, the oxidation process in the DCVA data were multiplied by –1. All experiments of N621 complex were measured in 1:1 actonitrile/tert-butanol solution containing 0.1 M TBAP using a piece of FTO glass as the working electrode with a scan rate of 100 mV/s .
3. CV of HW456/TiO2 films 3000
6
i x 10 (A)
2000
1000
0
-1000
-2000 -0.3
0.0
0.3
0.6
0.9
1.2
+
E vs Fc/FC (V)
Figure S3 Cyclic voltammogram of HW456 on nanocrystalline TiO2 film at a scan rate of 100mV/s in non-aqueous solution (0.1 M TBAP in acetonitrile).
2
2. Mercury interaction with –NCS ligands in dyes N621 and HW456 4000
500 3500
400 3000 2500
200
2000
6
i x 10 (A)
6
i x 10 (A)
300
100
1500
0
1000
-100
500
-200
0
-300
-500
-0.4
-0.2
0.0
0.2
0.4 +
E vs Fc/Fc (V)
(a)
0.6
0.8
-0.4
-0.2
0.0
0.2
0.4
+
E vs Fc/Fc (V)
(b)
Figure S4 Cyclic voltammetry in the absence (solid line) and presence (dash) of mercury for (a) N621 and (b) HW456 on nanocrystalline TiO2 film at a scan rate of 1 V/s in non-aqueous solution (0.1 M TBAP in acetonitrile).
3
