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Polyaniline derivatives represent one of the most widely used classes of conductive polymers. The fundamentally important electronic properties of pernigraniline salts, the fully oxidized and acid-doped derivatives of polyanilines, however, are still not well-understood due to their poor stability and configurational uncertainty. To address these issues and to synthetically access stable analogues of pernigraniline salts, ladder-type constitution was imparted into a series of model oligomer analogues with rigid backbones constituted by up to 27 fused rings. The syntheses were achieved through iterative cross-coupling reactions followed by cyclization and oxidation. In contrast to their unstable non-ladder-type counterparts, these ladder-type pernigraniline-like molecules all adopt a well-defined all- trans configuration and demonstrate an excellent chemical stability after protonation, rendering it possible to reveal the intrinsic electronic and magnetic properties of molecules resembling pernigraniline. Protonated salts of these oligomers feature a significant diradicaloid open-shell resonance contribution. A dominant temperature-independent Pauli paramagnetism was observed in the solid state, an indication of the delocalization nature of the polarons in ladder-type analogues of pernigraniline salt.

Singlet exciton fission is a spin-allowed process to generate two triplet excitons from a single absorbed photon. This phenomenon offers great potential in organic photovoltaics, but the mechanism remains poorly understood. Most reports to date have addressed intermolecular fission within small-molecular crystals. However, through appropriate chemical design chromophores capable of intramolecular fission can also be produced. Here we directly observe sub-100 fs activated singlet fission in a semiconducting poly(thienylenevinylene). We demonstrate that fission proceeds directly from the initial 1Bu exciton, contrary to current models that involve the lower-lying 2Ag exciton. In solution, the generated triplet pairs rapidly recombine and decay through the 2Ag state. In films, exciton diffusion breaks this symmetry and we observe long-lived triplets which form charge-transfer states in photovoltaic blends.

The improvement of the power conversion efficiency (PCE) of polymer bulk heterojunction (BHJ) solar cells has generally been achieved through synthetic design to control frontier molecular orbital energies and molecular ordering of the electron-donating polymer. An alternate approach to control the PCE of a BHJ is to tune the miscibility of the fullerene and a semiconducting polymer by varying the structure of the fullerene. The miscibility of a series of 1,4-fullerene adducts in the semiconducting polymer, poly(3-hexylselenophene), P3HS, was measured by dynamic secondary ion mass spectrometry using a model bilayer structure. The microstructure of the bilayer was investigated using high-angle annular dark-field scanning transmission microscopy and linked to the polymer-fullerene miscibility. Finally, P3HS:fullerene BHJ solar cells were fabricated from each fullerene derivative, enabling the correlation of the active layer microstructure to the charge collection efficiency and resulting PCE of each system. The volume fraction of polymer-rich, fullerene-rich, and polymer-fullerene mixed domains can be tuned using the miscibility leading to improvement in the charge collection efficiency and PCE in P3HS:fullerene BHJ solar cells. These results suggest a rational approach to the design of fullerenes for improved BHJ solar cells.