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Energy collection in photosynthetic microorganisms occurs through vectorial energy transfer along organized assemblies of chromophores. This process has inspired many research groups and yielded numerous examples of self-assembled photoactive structures. Dye sensitization of solar cells usually requires covalent anchoring of dyes onto the surface of metal oxides. A new porphyrin derivative that self-assembles upon non-covalent interaction with a surface has been designed and characterized by AFM. Interaction with metal oxide surfaces is further documented by the sensitization of metal oxide surfaces and the generation of photocurrent in non-optimized dye sensitized solar cells.

Two porphyrin dyads with the donor-π-acceptor molecular architecture, namely (ZnP)-[triazine-gly]-(H₂PCOOH) and (ZnP)-[triazine-Npip]-(H₂PCOOH), which consist of a zinc-metalated porphyrin unit and a free-base porphyrin unit covalently linked at their peripheries to a central triazine group, substituted either by a glycine in the former or a N-piperidine group in the latter, have been synthesized via consecutive amination substitution reactions of cyanuric chloride. The UV-vis absorption spectra and cyclic-voltammetry measurements of the two dyads, as well as theoretical calculations based on Density Functional Theory, suggest that they have suitable frontier orbital energy levels for use as sensitizers in dye-sensitized solar cells. Dye-sensitized solar cells based on (ZnP)-[triazine-gly]-(H₂PCOOH) and (ZnP)-[triazine-Npip]-(H₂PCOOH) have been fabricated, and they were found to exhibit power conversion efficiency values of 5.44 and 4.15%, respectively. Photovoltaic measurements (J–V curves) and incident photon to current conversion efficiency spectra of the two solar cells suggest that the higher power conversion efficiency value of the former solar cell is a result of its enhanced short circuit current, open circuit voltage, and fill factor values, as well as higher dye loading. This is ascribed to the existence of two carboxylic acid anchoring groups in (ZnP)-[triazine-gly]-(H₂PCOOH), compared to one carboxylic acid group in (ZnP)-[triazine-Npip]-(H₂PCOOH), which leads to a more effective binding onto the TiO₂ photoanode. Electrochemical impedance spectra show evidence that the (ZnP)-[triazine-gly]-(H₂PCOOH) based solar cell exhibits a longer electron lifetime and more effective suppression of charge recombination reactions between the injected electrons and electrolyte.

A series of tetraphenyl meso-substituted porphyrins with either p-amino or p-carboxy substituents has been studied as dyes for standard dye-sensitized solar cells (DSSCs). The porphyrins with greater numbers of amino groups generally show greater efficiency, primarily due to higher photocurrents; open-circuit voltage and fill factors are comparable. The most efficient sensitizer was the trans disubstituted zinc porphyrin, with an overall solar energy conversion efficiency of 5.66%, slightly higher than the triamino zinc porphyrin at 5.18%. The improved efficiency is attributed to the well known push–pull effect in porphyrinsensitized DSSCs with electrondonating groups opposite to the electronwithdrawing anchoring (carboxy) groups. It is suggested that porphyrin derivatives with cis diaminophenyl groups show somewhat diminished efficiency due to difficulties with regeneration of the dye from its oxidized form.

A new copper phthalocyanine, namely 9(10),16(17),23(24)-tri-tert-butyl-2-[acetynyl-(4-carboxy)phenyl]phthalocyaninatocopper and its related free base have been synthesized as potential stable blue dyes for dye sensitized solar cells. The molecule structure consists on an unsymmetrically-substituted macrocycle bearing three tert-butyl groups and one phenylethynyl moiety as peripheral substituents and it is analogue to that of a previously published zinc derivative. Chemical and optical characterizations, as well as theoretical calculations of the frontier orbitals of both molecules are discussed. To evaluate the effect of the central metal on the photovoltaic behavior of this dye, the novel molecules have been both tested and confronted with the zinc derivative. This last one has shown efficiency values significantly higher than those previously published with a 2.10% maximum efficiency, while the other two dyes yielded 1.66% and 1.38% maximum efficiency respectively.

In this contribution, different porphyrin derivatives were experimentally synthesized and theoretically analyzed using several electronic structure methods to study the geometrical and electronic properties of A₄, trans-A₂B${}_2$and A₃B porphyrins bearing several functional groups (–OH, –COOH, -3,5-di-$t$Bu, –OCH₂CH₂CH₂COOEt and –OMe) suitable to be employed as dyes in Dye Sensitized Solar Cells (DSSC). A₄ (R $=$ -H, -OMe, -OH, -3,5-di-tert-butyl, –OCH₂CH₂CH₂COOEt) and A₃B (R${}_1=$R${}_2=$R${}_3=$–H; R${}_4=$–OH and R${}_4=$-3,5-di-$t$Bu) porphyrins were synthesized and characterized by UV-vis and ¹H NMR spectroscopies for comparison. The geometrical parameters were analyzed in the ground state and gas phase using the semiempirical method PM6 and the DFT functionals M06-2X and B3LYP, in combination with the 6-31G(d), DZVP and TZVP basis set. For calculations of the electronic and excited state properties, CAM-B3LYP, M06-2X and HSE06, using SMD as solvation model, were applied. This study revealed that HSE06/DZVP protocol is the best methodology to simulate electronic spectra in these porphyrin derivatives. Indeed, whereas substituent groups did not significantly affect the geometrical structure of the porphyrin derivatives studied, they do influence their electronic structures, mainly in the LUMO (lowest unoccupied molecular orbital) energy levels.

The first example of A2B2 tetrabenzoporphyrin (KW-4) was synthesized, characterized and evaluated as a sensitizer for dye-sensitized solar cells. UV-vis and fluorescence spectroscopy revealed red-shifted and broadened absorption spectra of A2B2 tetrabenzoporphyrin as compared with its A2 dibenzo- and A2B2 dibenzoporphyrin analogues, which is a desired feature of dyes for dye-sensitized solar cells. DFT calculations also indicate favorable electron density distribution on the HOMO and LUMO of KW-4. However, the power conversion efficiency of the solar cell based on tetrabenzoporphyrin KW-4 displayed inferior performance than that of the solar cell based on A2 dibenzoporphyrin KW-2. The lower performance of the KW-4 cell was ascribed to two factors: the low lying LUMO energy level leading to less efficient electron injection and the “flat geometry” of the dye on TiO₂ surface facilitating charge recombination and decreasing dye loading. The investigation of anchoring group effect suggests that the acrylic acid group is a better anchoring group than pentadienyl carboxylic acid.