Stable organic semiconductors are critical to produce inexpensive, efficient and flexible thin film organic solar cells. A current chemical focus is the synthesis of stable, electron-accepting materials to be utilized as an acceptor layer in photovoltaics.1 The Anthony group has shown that the functionalization of pentacene with suitable electron withdrawing groups provides a catalog of suitable acceptors for this purpose.2 These pentacenes can be further modified to pack in a unique 1-dimensional "sandwich herringbone" crystal packing, leading to improved device current.3 To improve the stability of acene acceptors, we have taken two hetero-atom themed approaches. First, we have studied the acenequinone as an electron-accepting chromophore.4 Further, we replaced the terminal aromatic rings with heterocycles, such as furan or thiophene. In order to enhance the crystal engineering versatility of the chromophore, we utilize c-fused heterocycles (rather than the more commonly used b-fused cycles seen in e.g. anthradithiophenes). The c-fused acenequinones can be tetra-functionalized with silylethynyl groups to influence crystal packing and increase solubility.5 The silylethyne groups are known to increase the photostability and lower the energy gap (Eg) of pentacenes.5 The functionalization of the silylethyne groups also aids in lowering the lowest unoccupied orbital (LUMO) of acene structures.5

A range of small molecules of interest for use in organic semiconductor devices were studied computationally. Trends in geometry, absorption spectra, molecular orbitals, electrostatic potentials, reorganisation energies were studied. Results suggest that, as with acenes, the performance of non-linear cata-condensed polyaromatic hydrocarbons improves as number of fused benzene rings increases. The torsion in these molecules did not appear to have a large impact on the conjugation across the core and little effect on the absorption spectra, although it did affect the reorganisation energies on which charge mobilities depend. Computational studies of mobilities of anthradithiophene molecules were broadly able to reproduce trends seen experimentally and emphasised the importance of crystal morphology. Experimental work was also carried out to search for cocrystals between anthradithiophene derivatives. Many examples were found with some mixtures forming different cocrystals at different mixture ratios. These results were rationalised by a computational study that showed molecules which had a similar binding energy were more likely to be able to form cocrystals. Cocrystal devices were fabricated and 3 out of 7 showed a larger mobility than devices made out of its constituent materials alone. The best of these had a mobility 65% higher than a device made out of the constituent material with the largest mobility. An energy decomposition analysis was carried out on a novel thallophilic system, a complex of thallium with a neutral β-triketimine ligand which was found to form dimers with close Tl-Tl interactions. Calculations show the electrostatic interaction to be repulsive for the dimer with no counter ions, but attractive when 3,5-bistrifluoromethylphenyl borate counter ions are included. This suggests the metallophilic interaction is counter ion-mediated, requiring the anions to provide favourable electrostatics, even in the case of spatially diffuse and distant counter ions such used here. To enable the studies described here software was written for simulating absorption spectra. An implementation into the Gaussian Suite of programs of an energy decomposition scheme and its extension to include an empirical dispersion correction was also carried out.