Tomás Torres

Covalent and noncovalent phthalocyanine-carbon nanostructure systems: synthesis, photoinduced electron transfer, and application to molecular photovoltaics

Photosynthesis is used by nature to convert light energy into chemical energy in some living systems. In such a process, a cascade of very efficient, short-range energy and electron transfer events between well-arranged, light-harvesting organic donor and acceptor pigments takes place within the photosynthetic reaction center, leading to the overall generation of chemical energy from sunlight with near quantum efficiency.1-8 During the past decade, a significant effort has been made by the scientific community toward the preparation of synthetic model compounds of natural photosynthetic systems able to convert light into other energy sources,9 probably fostered by the increasing concerns related to the utilization of fossils fuels for the production of electricity in terms of both availability and environmental issues. However, considering the structural complexity presented by the natural photosynthetic systems, much of the scientific effort has been devoted toward the preparation and study of structurally simpler systems, with the aim of reproducing some of the fundamental steps occurring in natural photosynthesis, one of the most important being the photoinduced charge separation (CS).10-12 Among the chromophores that have been used as molecular components in artificial photosynthetic systems, porphyrinoids, the ubiquitous molecular building blocks employed by nature in natural photosynthesis, have been the preferred and obvious choice, due to their intense optical absorption and rich redox chemistry.13-20 Within the large family of porphyrinoid systems, phthalocyanines (Pcs) enjoy a privileged position (Figure 1a). These chromophores, which have a two-dimensional 18-πelectron aromatic system isoelectronic with that of porphyrins (Pors), possess in fact unique physicochemical properties which render these macrocycles valuable building blocks in materials science.21-32 Pcs are thermally and chemically stable compounds which present an intense absorption in the red/near-infrared (IR) region of the solar spectrum with extinction coefficients (as high as 200 000 M-1 cm-1) and fluorescence quantum yields * To whom correspondence should be addressed. E-mail: tomas.torres@uam.es (T.T.); dirk.guldi@chemie.uni-erlangen.de (D.M.G.). † Universidad Autonoma de Madrid. ‡ Friedrich-Alexander-Universitat Erlangen-Nurnberg. § IMDEA-Nanociencia. Chem. Rev. 2010, 110, 6768–6816 6768

Phthalocyanines: old dyes, new materials. Putting color in nanotechnology

Phthalocyanines are versatile building blocks for fabricating materials at the nanometer scale. These colored macrocycles exhibit fascinating physical properties which arise from their delocalized pi-electronic structure. This article describes why these molecules are targets for different scientific purposes and technological applications.

Meso-substituted porphyrins for dye-sensitized solar cells.

Among the several approaches for harnessing solar energy and converting it into electricity, dye-sensitized solar cells (DSSC) represent one of the most promising methods for future large-scale power production from renewable energy sources. In these cells, the sensitizer is one of the key components harvesting solar radiation and converting it into electric current. The electrochemical, photophysical, and ground and excited state properties of the sensitizer play an important role for charge transfer dynamics at the semiconductor interface. Moreover, for long-term stability and practical applications, electrolytes based on the iodine/triiodine couple also suffer from two other disadvantages: the corrosive effect toward the metal electrodes, and the partial absorption of the visible light by triiodine anions. These issues hence constitute one of the reasons that have encouraged the development of alternative iodine-free redox couples in liquid electrolytes for DSSCs.

Phthalocyanines and related compounds:organic targets for nonlinear optical applications

Phthalocyanines (Pcs) and related compounds with their extended two-dimensional pi;-electronic delocalization are important targets to study nonlinear optical responses. The tailorability of these macrocycles allows the fine-tuning of the chemical structure and nonlinear optical response. In this article, the design and main properties of phthalocyanines for second- and third-order nonlinear optical (NLO) and optical limiting applications are discussed, both at the microscopic and macroscopic level. The points of view of synthetic organic chemists and physicists are accorded, the main aim of the review being to highlight the key problems of the field and place them within the general context of NLO materials.

Phthalocyanines: From outstanding electronic properties to emerging applications†

This review paper gives a brief overview on how the outstanding chemical and physical properties of phthalocyanines and phthalocyanine derivatives are being studied and employed in order to construct state-of-the-art technological devices. In a first instance, a short account on how the nature of the phthalocyanine structure and its organization in condensed phases play an important role in their conducting and ultraviolet-visible absorption properties is presented. Consequently, these basic electronic and photophysical features of phthalocyanines allow us to explain why phthalocyanine-based multicomponent covalent or noncovalent donor-acceptor systems may give rise to very interesting photophysical properties, in particular in terms of their ability to generate very long-lived photoinduced charge-separated states. A concise survey on the organization of these multifunctional systems shows how a profound understanding of the morphology at the nanometer-scale of these phthalocyanine-based molecular materials is needed in order to control their physical properties in condensed phases. All the previously mentioned chemical and physical features combined together led us to the description of the latest attempts at incorporating phthalocyanines into photovoltaic devices for solar energy conversion and onto quantum dots for photodynamic therapy or quantum computing.

Catalysis of Recombination and Its Limitation on Open Circuit Voltage for Dye Sensitized Photovoltaic Cells Using Phthalocyanine Dyes

In order to increase the energy efficiency of dye-sensitized solar cells beyond 10%, an improved dye needs to be developed with greater light absorption in the red and near-infrared. Many dyes have been tested for this purpose; however, no dye with significant absorption beyond 750 nm has functioned properly. We have examined a series of ruthenium phthalocyanines, a dye class with large and tunable absorption in the red. For these dyes we observe a large reduction in the output voltage of the cells relative to the benchmark dye (N719). By examination of photovoltage transients and charge density measurements, we demonstrate that this reduction in voltage is caused by a 100-fold increase in the rate constant for recombination (iodine reduction) at the TiO2/electrolyte interface. N719, however, does not seem to catalyze this reaction. By examination of the literature, we propose that catalysis of the recombination reaction may be occurring for many other classes of potentially useful dyes including porphyri...

Facile Decoration of Functionalized Single-Wall Carbon Nanotubes with Phthalocyanines via Click Chemistry

We describe the functionalization of single-wall carbon nanotubes (SWNTs) with 4-(2-trimethylsilyl)ethynylaniline and the subsequent attachment of a zinc-phthalocyanine (ZnPc) derivative using the reliable Huisgen 1,3-dipolar cycloaddition. The motivation of this study was the preparation of a nanotube-based platform which allows the facile fabrication of more complex functional nanometer-scale structures, such as a SWNT-ZnPc hybrid. The nanotube derivatives described here were fully characterized by a combination of analytical techniques such as Raman, absorption and emission spectroscopy, atomic force and scanning electron microscopy (AFM and SEM), and thermogravimetric analysis (TGA). The SWNT-ZnPc nanoconjugate was also investigated with a series of steady-state and time-resolved spectroscopy experiments, and a photoinduced communication between the two photoactive components (i.e., SWNT and ZnPc) was identified. Such beneficial features lead to monochromatic internal photoconversion efficiencies of 17.3% when the SWNT-ZnPc hybrid material was tested as photoactive material in an ITO photoanode.

Effect of Coadsorbent on the Photovoltaic Performance of Zinc Pthalocyanine-Sensitized Solar Cells

The effect of chenodeoxycholic acid as a coadsorbent on TiO 2 nanocrystalline solar cells incorporating phthalocyanine sensitizers was studied under various conditions. Adding chenodeoxycholic acid onto TiO 2 nanoparticles not only reduces the adsorption of phthalocyanine sensitizers but also prevents sensitizer aggregation, leading to different photovoltaic performance. The inspection of IPCE and absorption spectra showed that the load of phthalocyanine sensitizers is strongly dependent on the molar concentration of chenodeoxycholic acid coadsorbent. The open circuit voltage of the solar cells with chenodeoxycholic acid coadsorbent increases due to the enhanced electron lifetime in TiO 2 nanoparticles coupled with the band edge shift of TiO 2 to negative potentials.

Long-lived photoinduced charge separation for solar cell applications in phthalocyanine-fulleropyrrolidine dyad thin films{

The photophysical properties of a new dyad molecule composed of a covalently linked Zn-phthalocyanine (antenna/donor) and a C60 derivative (acceptor) have been investigated. We report experimental evidence of long-lived charge separation in the solid state with a lifetime several orders of magnitude higher than in solution. Such a long lifetime, unusual for phthalocyanine–fullerene dyads, is the basis for possible photovoltaic applications. A first demonstration of a working solar cell using phthalocyanine–fullerene dyads as the active material is presented. Though the power conversion efficiency under simulated solar illumination of 80 mW cm−2 is found to be moderate (0.02%), it is an encouraging result for application of C60 dyad molecules to photovoltaics.

Phthalocyanines and Phthalocyanine Analogues: The Quest for Applicable Optical Properties

Summary. The central subject of this article is the description of the current work of the authors in the context of the Cost Action 518, project DE-1, and the Phthalocyanines Research Training Network, both financed by the European Community. The aim of the above projects is the design, synthesis, and structural and physical characterization of molecular and polymeric materials based on phthalocyanine derivatives with particular optical properties, as well as the study of their technological applications in the sensors field.