Characterization of Excited-State Electronic Structure in Diblock π-Conjugated Oligomers with Adjustable Linker Electronic Coupling.

Diblock conjugated oligomers are π-conjugated molecules that contain two segments having distinct frontier orbital energies and HOMO-LUMO gap offsets. These oligomers are of fundamental interest to understand how the distinct π-conjugated segments interact and modify their excited state properties. The current paper reports a study of two series of diblock oligomers that contain oligothiophene (Tn) and 4,7-bis(2-thienyl)-2,1,3-benzothiadiazole (TBT) segments that are coupled by either ethynyl (-C≡C-) or trans-(-C≡C-)2Pt(II)(PBu3)2 acetylide linkers. In these structures, the Tn segment is electron rich (donor), and the TBT is electron poor (acceptor). The diblock oligomers are characterized by steady-state and time-resolved spectroscopy, including UV-visible absorption, fluorescence, fluorescence lifetimes, and ultrafast transient absorption spectroscopy. Studies are compared in several solvents of different polarity and with different excitation wavelengths. The results reveal that the (-C≡C-) linked oligomers feature a delocalized excited state that takes on a charge transfer (CT) character in more polar media. In the (-C≡C-)2Pt(II)(PBu3)2-linked oligomers, there is weak coupling between the Tn and TBT segments. Consequently, short wavelength excitation selectively excites the Tn segment, which then undergoes ultrafast energy transfer (~1 ps) to afford a TBT-localized excited state.

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

A series of diblock oligomers containing oligothiophene (Tn, 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 Tn 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.

Synthesis, Electrochemistry, and Spectroscopy of Blue Platinum(II) Polyynes and Diynes.

The smallest band gap observed so far (1.77 eV) for an organometallic polymer is exhibited by the blue, rigid-rod polymer 2, which is prepared by the reaction of trans-[PtCl2 (PnBu3 )2 ] with one equivalent of 1.