Athanassios G. Coutsolelos

Promising Fast Energy Transfer System via an Easy Synthesis: Bodipy–Porphyrin Dyads Connected via a Cyanuric Chloride Bridge, Their Synthesis, and Electrochemical and Photophysical Investigations

The boron dipyrrin (Bodipy) chromophore was combined with either a free-base or a Zn porphyrin moiety (H(2)P and ZnP respectively), via an easy synthesis involving a cyanuric chloride bridging unit, yielding dyads Bodipy-H(2)P (4) and Bodipy-ZnP (5). The photophysical properties of Bodipy-H(2)P (4) and Bodipy-ZnP (5) were investigated by UV-Vis absorption and emission spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. The comparison of the absorption spectra and cyclic voltammograms of dyads Bodipy-H(2)P (4) and Bodipy-ZnP (5) with those of their model compounds Bodipy, H(2)P, and ZnP shows that the spectroscopic and electrochemical properties of the constituent chromophores are essentially retained in the dyads indicating negligible interaction between them in the ground state. In addition, luminescence and transient absorption experiments show that excitation of the Bodipy unit in Bodipy-H(2)P (4) and Bodipy-ZnP (5) into its first singlet excited state results in rapid Bodipy to porphyrin energy transfer-k(4) = 2.9 × 10(10) s(-1) and k(5) = 2.2 × 10(10) s(-1) for Bodipy-H(2)P (4) and Bodipy-ZnP (5), respectively-generating the first porphyrin-based singlet excited state. The porphyrin-based singlet excited states give rise to fluorescence or undergo intersystem crossing to the corresponding triplet excited states. The title complexes could also be used as precursors for further substitution on the third chlorine atom on the cyanuric acid moiety.

The importance of various anchoring groups attached on porphyrins as potential dyes for DSSC applications

In the design of new chromophores, with high efficiency, chemical stability and low cost materials for dye sensitized solar cells, porphyrin macrocycles could play a very important role. Their successful use in nature during photosynthesis must be the inspiration for new artificial antenna systems. Porphyrins offer an excellent platform for building such multi-chromophoric systems to self-assemble because of the availability of several substituent sites and their intrinsic spectroscopic properties. Specifically, their high absorption ability in the visible region can be extended, and electron donor and anchoring groups with high chemical affinity to the cell should be part of the new design. This review provides a summary of some of the most important developments and approaches that are used in order to improve the light collection efficiency of DSSCs based on porphyrin hybrid derivatives. For this reason we have attempted to describe the developments in the DSSCs of various porphyrin dyes with different anchoring groups linked through either meso or β-positions. Also, the influence of the anchoring groups in the cell performance is discussed. Studies containing chromophores other than porphyrin derivatives are not included in this work.

Electron vs Energy Transfer in Arrays Featuring Two Bodipy Chromophores Axially Bound to a Sn(IV) Porphyrin via a Phenolate or Benzoate Bridge

In this report we describe the synthesis of multichromophore arrays consisting of two Bodipy units axially bound to a Sn(IV) porphyrin center either via a phenolate (3) or via a carboxylate (6) functionality. Absorption spectra and electrochemical studies show that the Bodipy and porphyrin chromophores interact weakly in the ground state. However, steady-state emission and excitation spectra at room temperature reveal that fluorescence from both the Bodipy and the porphyrin of 3 are strongly quenched suggesting that, in the excited state, energy and/or electron transfer might occur. Indeed, as transient absorption experiments show, selective excitation of Bodipy in 3 results in a rapid decay (τ ≈ 2 ps) of the Bodipy-based singlet excited state and a concomitant rise of a charge-separated state evolving from the porphyrin-based singlet excited state. In contrast, room-temperature emission studies on 6 show strong quenching of the Bodipy-based fluorescence leading to sensitized emission from the porphyrin moiety due to a transduction of the singlet excited state energy from Bodipy to the porphyrin. Emission experiments at 77 K in frozen toluene reveal that the room-temperature electron transfer pathway observed in 3 is suppressed. Instead, Bodipy excitation in 3 and 6 results in population of the first singlet excited state of the porphyrin chromophore. Subsequently, intersystem crossing leads to the porphyrin-based triplet excited state.

Photophysical, electrochemical and photovoltaic properties of dye sensitized solar cells using a series of pyridyl functionalized porphyrin dyes

Three porphyrin dyes, P1, P2 and P3, bearing one, two and four pyridyl groups, respectively, in the meso positions, acting as electron acceptor anchoring groups, were synthesized, characterized and investigated as sensitizers for the fabrication of dye sensitized solar cells (DSSCs). The overall power conversion efficiencies (PCEs) of DSSCs based on these dyes lay in the range 2.46–3.9% using a 12 μm thick TiO2 photoanode. Porphyrin P2 achieved the maximum performance, which can be rationalized by the high dye loading, efficient electron injection, dye regeneration process and longer electron lifetime, as demonstrated by the electrochemical impedance spectroscopy (EIS) measurements. The PCE of the DSSC based on the P2 sensitizer when the photoanode was treated with formic acid, showed an enhanced efficiency of 5.23%. This improvement, attributed to multifunctional properties such as higher dye uptake, reduced recombination process and enhanced charge collection efficiency. Deoxycholic acid (DCA) was also used as a coadsorbent in order to prevent dye aggregation and it was found that the PCE improved up to 6.12% for sensitizer P2 and the modified TiO2 photoanode, which can be attributed to further improvement in the electron injection efficiency and charge collection efficiency.

Enhancement of power conversion efficiency of dye-sensitized solar cells by co-sensitization of zinc-porphyrin and thiocyanate-free ruthenium(II)-terpyridine dyes and graphene modified TiO2 photoanode

A combination of a meso substituted zinc-porphyrin with two pyridyl groups and two benzoate groups at cis positions to each other (POR) with a mononuclear ruthenium(II) complex containing a 2,6-bis(1-methylbenzimidazol-2-yl)pyridine ligand and a carboxylic acid functionalized terpyridine ligand (SPS-G3) has been used as co-sensitizing system for the fabrication of dye-sensitized solar cells (DSSCs). The POR/SPS-G3 co-sensitized solar cell with a TiO2 photoanode displays enhanced short circuit current, open circuit voltage, and fill factor values (Jsc = 16.18 mA cm−2, Voc = 0.64 V, FF = 0.71, respectively), resulting in an overall power conversion efficiency (PCE) of 7.35%, which is superior to that for the DSSCs based on the individual dyes POR and SPS-G3. This is attributed to the improved light harvesting efficiency of the POR/SPS-G3 co-sensitizing system, which is evidenced by the incident photon-to-current efficiency (IPCE) spectrum of the co-sensitized solar cell. Further improvement of the PCE value of the co-sensitized solar cell (up to 8.15%) has been achieved by using a graphene modified TiO2 (G-TiO2) photoanode, instead of a pure TiO2 photoanode. Based on dark current measurements and electrochemical impedance spectra (EIS), the increased PCE value of the solar cell with the G-TiO2 photoanode can be attributed to suppression of charge recombination at the photoanode/dye/electrolyte interface and enhancement of electron transport in the photoanode. These results are in accordance with the longer electron lifetime exhibited by the G-TiO2 photoanode.

Porphyrin oriented self-assembled nanostructures for efficient exciton dissociation in high-performing organic photovoltaics

Herein we report on enhanced organic solar cell performance through the incorporation of cathode interfacial layers consisting of self-organized porphyrin nanostructures with a face-on configuration. In particular, a water/methanol-soluble porphyrin molecule, the free base meso-tetrakis(1-methylpyridinium-4-yl)porphyrin chloride, is employed as a novel cathode interlayer in bulk heterojunction organic photovoltaics. It is demonstrated that the self-organization of this porphyrin compound into aggregates in which molecules adopt a face-to-face orientation parallel to the organic semiconducting substrate induces a large local interfacial electric field that results in a significant enhancement of exciton dissociation. Consequently, enhanced photocurrent and open circuit voltage were obtained resulting in overall device efficiency improvement in organic photovoltaics based on bulk heterojunction mixtures of different polymeric donors and fullerene acceptors, regardless of the specific combination of donor–acceptor employed. To highlight the impact of molecular orientation a second porphyrin compound, the Zn-metallated meso-tetrakis(1-methylpyridinium-4-yl)porphyrin chloride, was also studied and it was found that it forms aggregates with an edge-to-edge molecular configuration inducing a smaller increase in the device performance.

Efficient sensitization of dye-sensitized solar cells by novel triazine-bridged porphyrin-porphyrin dyads.

Two novel porphyrin-porphyrin dyads, the symmetrical Zn[Porph]-Zn[Porph] (2) and unsymmetrical Zn[Porph]-H2[Porph] (4), where Zn[Porph] and H2[Porph] are the metalated and free-base forms of 5-(4-aminophenyl)-10,15,20-triphenylporphyrin, respectively, in which two porphyrin units are covalently bridged by 1,3,5-triazine, have been synthesized via the stepwise amination of cyanuric chloride. The dyads are also functionalized by a terminal carboxylic acid group of a glycine moiety attached to the triazine group. Photophysical measurements of 2 and 4 showed broaden and strengthened absorptions in their visible spectra, while electrochemistry experiments and density functional theory calculations revealed negligible interaction between the two porphyrin units in their ground states but appropriate frontier orbital energy levels for use in dye-sensitized solar cells (DSSCs). The 2- and 4-based solar cells have been fabricated and found to exhibit power conversion efficiencies (PCEs) of 3.61% and 4.46%, respectively (under an illumination intensity of 100 mW/cm(2) with TiO2 films of 10 μm thickness). The higher PCE value of the 4-based DSSC, as revealed by photovoltaic measurements (J-V curves) and incident photon-to-current conversion efficiency (IPCE) spectra of the two cells, is attributed to its enhanced short-circuit current (J(sc)) under illumination, high open-circuit voltage (V(oc)), and fill factor (FF) values. Electrochemical impedance spectra demonstrated shorter electron-transport time (τd), longer electron lifetime (τe), and high charge recombination resistance for the 4-based cell, as well as larger dye loading onto TiO2.

Meso-substituted porphyrin derivatives via palladium-catalyzed amination showing wide range visible absorption: synthesis and photophysical studies.

In recent years, there has been a growing interest in the design and synthesis of chromophores, which absorb in a wide region of the visible spectrum, as these constitute promising candidates for use as sensitizers in various solar energy conversion schemes. In this work, a palladium-catalyzed coupling reaction was employed in the synthesis of molecular triads in which two porphyrin or boron dipyrrin (BDP) chromophores are linked to the meso positions of a central Zn porphyrin (PZn) ring via an amino group. In the resulting conjugates, which strongly absorb over most of the visible region, the electronic properties of the constituent chromophores are largely retained while detailed emission experiments reveal the energy transfer pathways that occur in each triad.

A new family of A2B2 type porphyrin derivatives: synthesis, physicochemical characterization and their application in dye-sensitized solar cells

A new series of A2B2 type porphyrins, i.e. free base P1 and Zn-complex P2, have been synthesized and characterized as photosensitizers for dye sensitized solar cells (DSSCs). These dye molecules contain a porphyrin unit as a π-spacer, two N,N′-dimethylphenyl groups as electron donors and two phenylcarboxylic acid moieties as anchoring groups yielding push push–pull pull type porphyrins. The photophysical as well as electrochemical properties of the two dyes (P1 and P2) were investigated by UV-Vis, fluorescence spectroscopy and cyclic voltammetry. The DFT results showed that the HOMO is located on the donor group and the LUMO is located on the anchoring carboxylate group indicating their suitability for fabrication in DSSCs. Under photovoltaic measurements, overall PCEs of 3.80% and 4.90% were achieved with the DSSCs based on P1 and P2 dyes, respectively. The overall PCEs have been further improved up to 4.83% and 6.07%, with P1 and P2 dyes when CDCA co-adsorbent was added to the dye solution. The electrochemical impedance data indicate that the electron lifetime was improved by the coadsorption of CDCA, which was attributed to the improvement in both Voc and Jsc. The increase in Jsc has also been attributed to the reduction of the back reaction, i.e. the recombination of electrons with tri-iodide ions.

Self‐Assembly Into Spheres of a Hybrid Diphenylalanine–Porphyrin: Increased Fluorescence Lifetime and Conserved Electronic Properties

A series of protected phenylalanine and diphenylalanine derivatives have been coupled through a peptide bond to a monoaminoporphyrin to form new materials. A comparative study in solution and in the solid state has been performed and confirmed new and interesting properties for the self-assembled hybrid materials while conserving the electronic properties of the chromophore. Thus, they are powerful candidates for use in dye-sensitized solar cells.