Excitation-Wavelength-Dependent Charge Injection and Hole Localization in Diblock Oligomers Anchored to TiO₂

A series of diblock oligomers containing oligothiophene (T, n = 4, 5) and 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadizole (TBT) segments, functionalized with carboxylic acid anchoring groups, were prepared and anchored to mesoporous TiO₂ films to study wavelength-dependent interfacial electron transfer mechanisms. Thin films of the surface-anchored diblock oligomers contained two absorption bands centered at 400 and 500 nm, corresponding to the T and TBT blocks, respectively. Pulsed-laser excitation of the oligomer-sensitized films yielded local excited-states that promoted electron injection into TiO₂. The injection pathway was dependent on the excitation wavelength, as electron injection occurred from the oligomer block that was locally excited. Recombination between the injected electron and the oxidized oligomer was sensitive to the bridging unit that separates the oligomer conjugated segments (-C≡C- vs trans-Pt(PBu₃)₂-). When the bridge facilitated strong coupling between the two blocks (-C≡C- bridge), the excitation wavelength had no effect on the recombination pathway, as the hole was delocalized over the entire oligomer. However, in the weak coupling case (Pt(PBu₃)₂- bridge), selective excitation resulted in wavelength-dependent hole localization that persisted to the μs time scale, providing control over the recombination pathway by varying the excitation wavelength. Dye-sensitized solar cells (DSSCs) were fabricated by using the diblock oligomers as sensitizers. The photocurrent action spectra were measured, and the absorbed photon-to-current efficiency (APCE) provided further insight into the electron-transfer mechanisms that are operative under continuous illumination.