Photophysical Properties of BODIPY Derivatives for the Implementation of Organic Solar Cells: A Computational Approach.

Solar cells based on organic compounds are a proven emergent alternative to conventional electrical energy generation. Here, we provide a computational study of power conversion efficiency optimization of boron dipyrromethene (BODIPY) derivatives by means of their associated open-circuit voltage, short-circuit density, and fill factor. In doing so, we compute for the derivatives' geometrical structures, energy levels of frontier molecular orbitals, absorption spectra, light collection efficiencies, and exciton binding energies via density functional theory (DFT) and time-dependent (TD)-DFT calculations. We fully characterize four D-π-A (BODIPY) molecular systems of high efficiency and improved J sc that are well suited for integration into bulk heterojunction (BHJ) organic solar cells as electron-donor materials in the active layer. Our results are twofold: we found that molecular complexes with a structural isoxazoline ring exhibit a higher power conversion efficiency (PCE), a useful result for improving the BHJ current, and, on the other hand, by considering the molecular systems as electron-acceptor materials, with P3HT as the electron donor in the active layer, we found a high PCE compound favorability with a pyrrolidine ring in its structure, in contrast to the molecular systems built with an isoxazoline ring. The theoretical characterization of the electronic properties of the BODIPY derivatives provided here, computed with a combination of ab initio methods and quantum models, can be readily applied to other sets of molecular complexes to hierarchize optimal power conversion efficiency.

Molecular Structure, Quantum Coherence, and Solvent Effects on the Ultrafast Electron Transport in BODIPY-C60 Derivatives.

Photoinduced electron transfer in multichromophore molecular systems is defined by a critical interplay between their core unit configuration (donor, molecular bridge, and acceptor) and their system-solvent coupling; these lead to energy and charge transport processes that are key in the design of molecular antennas for efficient light harvesting and organic photovoltaics. Here, we quantify the ultrafast non-Markovian dissipative dynamics of electron transfer in D-π-A molecular photosystems comprising 1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene (BODIPY), Zn-porphyrin, fulleropyrrolidine, and fulleroisoxazoline. We find that the stabilization energy of the charge transfer states exhibits a significant variation for different polar (methanol, tetrahydrofuran (THF)) and nonpolar (toluene) environments and determine such sensitivity according to the molecular structure and the electron-vibration couplings that arise at room temperature. For the considered donor-acceptor (D-A) dyads, we show that the stronger the molecule-solvent coupling, the larger the electron transfer rates, regardless of the dyads' electronic coherence properties. We find such coupling strengths to be the largest (lowest) for methanol (toluene), with an electron transfer rate difference of 2 orders of magnitude between the polar and nonpolar solvents. For the considered donor-bridge-acceptor (D-B-A) triads, the molecular bridge introduces an intermediate state that allows the realization of Λ or cascaded-type energy mechanisms. We show that the latter configuration, obtained for BDP-ZnP-[PyrC60] in methanol, exhibits the highest transfer rate of all of the computed triads. Remarkably, and in contrast with the dyads, we show that the larger charge transfer rates are obtained for triads that exhibit prolonged electron coherence and population oscillations.

Room temperature quantum coherence vs. electron transfer in a rhodanine derivative chromophore.

Understanding electron transfer in organic molecules is of great interest in quantum materials for light harvesting, energy conversion and integration of molecules into solar cells. This, however, poses the challenge of designing specific optimal molecular structure for which the processes of ultrafast quantum coherence and electron transport are not so well understood. In this work, we investigate subpicosecond time scale quantum dynamics and electron transfer in an efficient electron acceptor rhodanine chromophoric complex. We consider an open quantum system approach to model the complex-solvent interaction, and compute the crossover from weak to strong dissipation on the reduced system dynamics for both a polar (methanol) and a non polar solvent (toluene). We show that the electron transfer rates are enhanced in the strong chromophore-solvent coupling regime, being the highest transfer rates those found at room temperature. Even though the computed dynamics are highly non-Markovian, and they may exhibit a quantum character up to hundreds of femtoseconds, we show that quantum coherence does not necessarily optimise the electron transfer in the chromophore.

Optical and Electronic Properties of Molecular Systems Derived from Rhodanine.

Push-pull functional compounds consisting of dicyanorhodanine derivatives have attracted a lot of interest because their optical, electronic, and charge transport properties make them useful as building blocks for organic photovoltaic implementations. The analysis of the frontier molecular orbitals shows that the vertical transitions of electronic absorption are characterized as intramolecular charge transfer; furthermore, we show that the analyzed compounds exhibit bathochromic displacements when comparing the presence (or absence) of solvent as an interacting medium. In comparison with materials defined by their energy of reorganization of electrons (holes) as electron (hole) transporters, we find a transport hierarchy whereby the molecule ( Z)-2-(1,1-dicyanomethylene)-5-[(4-dimethylamino)benzylidene]-1,3-thiazol-4 is better at transporting holes than molecule ( Z)-2-(1,1-dicyanomethylene)-5-(tetrathiafulvalene-2-ylidene)-1,3-thiazol-4.