Excitation-Wavelength-Dependent Photoinduced Electron Transfer in a π-Conjugated Diblock Oligomer

Control of photoinduced electron transfer through selective excitation of a π-conjugated diblock oligomeric system featuring tetrathiophene (T₄) and tetra(phenylene ethynylene) (PE₄) donor blocks capped with a naphthalene diimide (NDI) acceptor (T₄PE₄NDI) is demonstrated. Each π-conjugated oligomeric segment has its own discrete ionization potential, electron affinity, and optical band gap which provides an absorption profile that has specific wavelengths that offer selective excitation of the PE₄ and T₄ blocks. Therefore, T₄PE₄NDI can be selectively excited to form a charge-separated state via ultrafast photoinduced electron transfer from the PE₄ segment to NDI when excited at 370 nm, but it does not produce a charge-separated state when excited at 420 nm (T₄). Picosecond transient absorption techniques were performed to probe the excited-state dynamics, revealing ultrafast charge separation (∼4 ps) occurring from the PE₄ segment to NDI when excited at 370 nm, followed by delocalization of the hole over the T₄ segment. On the contrary, electron transfer is suppressed with excitation at longer wavelengths (≥420 nm), where the spectrum is dominated by the T₄ unit. The rate of electron transfer and charge recombination was investigated versus the length of the PE bridge unit in oligomers featuring zero and two PE units (T₄NDI and T₄PE₂NDI). The rate of charge recombination decreases from 1.2 × 10¹¹ to 1.0 × 10⁹ s^-1 with increasing bridge length between the T₄ and NDI components (T₄NDI to T₄PE₄NDI). Furthermore, wavelength-dependent photoinduced electron transfer was not observed in either T₄NDI or T₄PE₂NDI due to an insufficient PE bridge length. This work demonstrates the ability to use optical wavelength to control photoinduced electron transfer in a fully π-conjugated oligomer.