We investigate singlet fission (SF) in heterodimers comprising a pentacene unit covalently bonded to another acene as we systematically vary the singlet and triplet pair energies. We find that these energies control the SF process, where dimers undergo SF provided that the resulting triplet pair energy is similar or lower in energy than the singlet state. In these systems the singlet energy is determined by the lower-energy chromophore, and the rate of SF is found to be relatively independent of the driving force. However, triplet pair recombination in these heterodimers follows the energy gap law. The ability to tune the energies of these materials provides a key strategy to study and design new SF materials—an important process for third-generation photovoltaics.

We investigate singlet fission (SF) in heterodimers comprising a pentacene unit covalently bonded to another acene as we systematically vary the singlet and triplet pair energies. We find that these energies control the SF process, where dimers undergo SF provided that the resulting triplet pair energy is similar or lower in energy than the singlet state. In these systems the singlet energy is determined by the lower-energy chromophore, and the rate of SF is found to be relatively independent of the driving force. However, triplet pair recombination in these heterodimers follows the energy gap law. The ability to tune the energies of these materials provides a key strategy to study and design new SF materials—an important process for third-generation photovoltaics.

The use of Rozen’s reagent (HOF⋅CH₃CN) to convert polythiophenes to polymers containing thiophene-1,1-dioxide (TDO) is described. The oxidation of polythiophenes can be controlled with this potent, yet orthogonal reagent under mild conditions. The oxidation of poly(3-alkylthiophenes) proceeds at room temperature in a matter of minutes, introducing up to 60 % TDO moieties in the polymer backbone. The resulting polymers have a markedly low-lying lowest unoccupied molecular orbital (LUMO), consequently exhibiting a small bandgap. This approach demonstrates that modulating the backbone electronic structure of well-defined polymers, rather than varying the monomers, is an efficient means of tuning the electronic properties of conjugated polymers.

The use of Rozen’s reagent (HOF⋅CH₃CN) to convert polythiophenes to polymers containing thiophene-1,1-dioxide (TDO) is described. The oxidation of polythiophenes can be controlled with this potent, yet orthogonal reagent under mild conditions. The oxidation of poly(3-alkylthiophenes) proceeds at room temperature in a matter of minutes, introducing up to 60 % TDO moieties in the polymer backbone. The resulting polymers have a markedly low-lying lowest unoccupied molecular orbital (LUMO), consequently exhibiting a small bandgap. This approach demonstrates that modulating the backbone electronic structure of well-defined polymers, rather than varying the monomers, is an efficient means of tuning the electronic properties of conjugated polymers.

Polymer Pen Lithography (PPL) uses an array of polymeric tips, typically composed of poly(dimethyl siloxane), to transfer ink onto a surface and create patterns of soft molecules with micrometer to nanometer feature dimensions. In this study, tip arrays were fabricated from poly(methyl methacrylate), poly([methyl methacrylate]-co-[butyl methacrylate]), and poly(3-mercaptopropylmethylsiloxane), and used to pattern 1-mercaptohexadecanoic acid onto Au surfaces to determine the fidelity of pattern transfer by PPL as a function of the mechanical properties of the materials. It was found that the dependence between the applied force and feature edge length correlates directly to the mechanical properties of each of the polymers used to fabricate the tip arrays, where stiffer polymers have a reduced dependence between the applied force and feature size. This study demonstrates that PPL tip arrays can be composed of a wide variety of materials whose choice is determined by the desired printing application. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013