Table 1 Photophysical and electrochemical properties of PPV, Ru1 and Ru2.

From: Photocathodes beyond NiO: charge transfer dynamics in a π-conjugated polymer functionalized with Ru photosensitizers

Structure

λabs

λem (ΦPL)a

τemb

E0–0c

Eox

Ered1

Ered2

Ered3

ΔGinj,ed

ΔGinj,he

PPV

485

553, 587* (0.43)

< 1

2.30

+ 0.73

− 1.67

–

–

–

–

Ru1

438, 476

646 (0.06)

150

2.17

+ 1.10

− 1.33

− 1.50

− 1.79

0.60i; 0.47ii; − 1.70iii

− 0.11i; − 0.24ii; − 2.41 iii

Ru2

430, 458

627 (0.02)

139

2.24

+ 0.82

− 1.65

− 1.96

− 2.2

0.25i; 0.19ii; − 2.26iii

0.14i; 0.08ii; − 2.16iii

  1. In nm. UV/vis absorption and emission measurements were measured in CHCl3. In V vs. Fc+/Fc. Cyclic voltammetry was carried out at a scan rate of 100 mV·s−1 and of 0.5 mM complex solutions in acetonitrile containing TBABF4 as supporting electrolyte.
  2. aQuantum yield (ΦPL) of PPV was determined using Fluorescein (0.1 M NaOH, ΦPL = 0.95) as reference46,47, while the quantum yields of Ru1 and Ru2 were determined using [Ru(bpy)3]2+ (in acetonitrile, ΦPL = 0.03) as reference23.
  3. bIn ns. Emission lifetime was measured using time-correlated single photon counting.
  4. cE0–0 (in V) is calculated from the crossing point of normalized absorption and emission spectra48.
  5. dIn eV. If only respective RuII complex is excited: ΔGinj,e = e[E(Ru+/*) − E(PPV0/−)], where E(Ru+/*) = E(Ru+/0) − E0–0; if only PPV is excited: ΔGinj,e = e[E(Ru+/0) − E(PPV*/−)], where E(PPV*/−) = E(PPV0/−) + E0–0; and if both PPV and Ru are excited: ΔGinj,e = e[E(Ru+/*) − E(PPV*/−)].
  6. eIn eV. If only Ru is excited: ΔGinj,h = e[E(PPV+/0) − E(Ru*/−)], where E(Ru*/−) = E(Ru0/−) + E0–0; if only PPV is excited: ΔGinj,h = e[E(PPV+/*) − E(Ru0/−)], where E(PPV+/*) = E(PPV+/0) − E0–0; and if both PPV and Ru are excited: ΔGinj,h = e[E(PPV+/*) − E(Ru*/−)].
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