Current organic semiconductors for organic photovoltaics (OPV) have relative dielectric constants (relative permittivities, ε r) in the range of 2–4. As a consequence, Coulombically bound electron‐hole pairs (excitons) are produced upon absorption of light, giving rise to limited power conversion efficiencies. We introduce a strategy to enhance ε r of well‐known donors and acceptors without breaking conjugation, degrading charge carrier mobility or altering the transport gap. The ability of ethylene glycol (EG) repeating units to rapidly reorient their dipoles with the charge redistributions in the environment was proven via density functional theory (DFT) calculations. Fullerene derivatives functionalized with triethylene glycol side chains were studied for the enhancement of ε r together with poly(p‐phenylene vinylene) and diketopyrrolopyrrole based polymers functionalized with similar side chains. The polymers showed a doubling of ε r with respect to their reference polymers in identical backbone. Fullerene derivatives presented enhancements up to 6 compared with phenyl‐C61‐butyric acid methyl ester (PCBM) as the reference. Importantly, the applied modifications did not affect the mobility of electrons and holes and provided excellent solubility in common organic solvents.

The invention of new organic materials with high dielectric constants is of extreme importance for the development of organic-based devices such as organic solar cells. We report on a synthetic way to increase the dielectric constant of fullerene derivatives. It is demonstrated that introducing triethylene glycol monoethyl ether (teg) side chains into fulleropyrrolidines increases the dielectric constant by ~46 percent without devaluation of optical properties, electron mobility and the energy level of the compound.

A multidisciplinary approach involving organic synthesis and theoretical chemistry is applied to investigate a promising strategy to improve charge separation in organic photovoltaics:installing permanent dipoles in fullerene derivatives. Firstly, a PCBM analogue with a permanent dipole in the side-chain (PCBDN) and its reference analogue without a permanent dipole (PCBBz) were successfully synthesised and characterised. Secondly, a multiscale modelling approach was applied to investigate if a PCBDN environment around a central donor-acceptor complex indeed facilitates charge separation. Alignment of the embedding dipoles in response to charges present on the central donor-acceptor complex enhances charge separation. The good correspondence between experimentally and theoretically determined electronic and optical properties of PCBDN, PCBBz and PCBM indicates that the theoretical analysis of the embedding effects of these molecules gives a reliable expectation for their influence on the charge separation process at a microscopic scale in a real device.This work suggests the following strategies to improve charge separation in organic photovoltaics: installing permanent dipoles in PCBM analogues and tuning the concentration of these molecules in an organic donor/acceptor blend.3

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