Giovanni Bottari

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

Photoinduced charge transfer and electrochemical properties of triphenylamine Ih-Sc3N@C80 donor-acceptor conjugates

Two isomeric [5,6]-pyrrolidine-I(h)-Sc(3)N@C(80) electron donor-acceptor conjugates containing triphenylamine (TPA) as the donor system were synthesized. Electrochemical and photophysical studies of the novel conjugates were made and compared with those of their C(60) analogues, in order to determine (i) the effect of the linkage position (N-substituted versus 2-substituted pyrrolidine) of the donor system in the formation of photoinduced charge separated states, (ii) the thermal stability toward the retro-cycloaddition reaction, and (iii) the effect of changing C(60) for I(h)-Sc(3)N@C(80) as the electron acceptor. It was found that when the donor is connected to the pyrrolidine nitrogen atom, the resulting dyad produces a significantly longer lived radical pair than the corresponding 2-substituted isomer for both the C(60) and I(h)-Sc(3)N@C(80) dyads. In addition to that, the N-substituted TPA-I(h)-Sc(3)N@C(80) dyad has much better thermal stability than the 2-substituted one. Finally, the I(h)-Sc(3)N@C(80) dyads have considerably longer lived charge separated states than their C(60) analogues, thus approving the advantage of using I(h)-Sc(3)N@C(80) instead of C(60) as the acceptor for the construction of fullerene based donor-acceptor conjugates. These findings are important for the design and future application of I(h)-Sc(3)N@C(80) dyads as materials for the construction of plastic organic solar cells.

Metal Nitride Cluster Fullerene M3N@C80 (M=Y, Sc) Based Dyads: Synthesis, and Electrochemical, Theoretical and Photophysical Studies

The first pyrrolidine and cyclopropane derivatives of the trimetallic nitride templated (TNT) endohedral metallofullerenes I(h)-Sc(3)N@C(80) and I(h)-Y(3)N@C(80) connected to an electron-donor unit (i.e., tetrathiafulvalene, phthalocyanine or ferrocene) were successfully prepared by 1,3-dipolar cycloaddition reactions of azomethine ylides and Bingel-Hirsch-type reactions. Electrochemical studies confirmed the formation of the [6,6] regioisomers for the Y(3)N@C(80)-based dyads and the [5,6] regioisomers in the case of Sc(3)N@C(80)-based dyads. Similar to other TNT endohedral metallofullerene systems previously synthesized, irreversible reductive behavior was observed for the [6,6]-Y(3)N@C(80)-based dyads, whereas the [5,6]-Sc(3)N@C(80)-based dyads exhibited reversible reductive electrochemistry. Density functional calculations were also carried out on these dyads confirming the importance of these structures as electron transfer model systems. Furthermore, photophysical investigations on a ferrocenyl-Sc(3)N@C(80)-fulleropyrrolidine dyad demonstrated the existence of a photoinduced electron-transfer process that yields a radical ion pair with a lifetime three times longer than that obtained for the analogous C(60) dyad.

Photoisomerization of a rotaxane hydrogen bonding template: Light-induced acceleration of a large amplitude rotational motion

Establishing methods for controlling aspects of large amplitude submolecular movements is a prerequisite for the development of artificial devices that function through rotary motion at the molecular level. Here we demonstrate that the rate of rotation of the interlocked components of fumaramide-derived [2]rotaxanes can be accelerated, by >6 orders of magnitude, by isomerizing them to the corresponding maleamide [2]rotaxanes by using light.

Functional Phthalocyanines: Synthesis, Nanostructuration, and Electro-Optical Applications

This overview focuses on the design and preparation of phthalocyanines (Pcs) and covers both fundamental synthetic approaches and more applied research. Thus, different topics including, e.g., the preparation of conjugated assemblies using Pcs as synthetic building blocks, the supramolecular organization of appropriately featured Pc-molecules, and the incorporation of Pcs into dendrimers and polymers, are discussed in this chapter. The second part of the review has been devoted to more technological aspects of these compounds covering Pc-based nanostructures and Pcs as active components of functional devices.

Phthalocyanine-Carbon Nanostructure Materials Assembled through Supramolecular Interactions.

The use of self-assembly for the construction of materials based on phthalocyanines and carbon nanostructures-fullerenes, single-walled carbon nanotubes, and graphene-has demonstrated to be a versatile strategy for the preparation of novel, multifunctional systems. Photophysical studies carried out on these photo- and electroactive supramolecular ensembles have revealed the occurrence of an efficient photoinduced electron-transfer process, thus paving the way for the utilization of these materials as active components in optoelectronic devices. This Perspective highlights the recent progress in the preparation of such materials and the potential use of these systems for the construction of nanostructured materials with singular physicochemical properties.

Phthalocyanines, subphthalocyanines and porphyrins for energy and electron transfer applications

The importance and complexity of energy and electron transfer reactions in biological and artificial light energy conversion systems have prompted the preparation and photophysical study of donor-acceptor (D-A) molecular models. This article aims to highlight the efforts of Portuguese and Spanish research groups on the design, synthesis and photophysical study of molecular and supramolecular donor-acceptor systems based on phthalocyanines, subphthalocyanines and porphyrins.

Amide-based molecular shuttles (2001-2006)*

Stimuli-responsive molecular shuttles are rotaxanes in which the macrocycle can be translocated from one position on the thread to a second site in response to an external trigger. Here, we present a brief overview of the contributions of the Leigh group to the field from 2001 to 2006. In this short period of time, molecular shuttles have moved from little more than laboratory curiosities to truly functional molecular machines.

Alkynyl-substituted phthalocyanines: versatile building blocks for molecular materials synthesis

Phthalocyanines are an interesting class of aromatic macrocycles which possess unique physical and chemical properties that make them excellent building blocks for the construction of molecular materials. Among the different functional groups that can be incorporated into the phthalocyanines skeleton, the alkynyl group is one of the most interesting; this is confirmed by the large number of organic synthetic materials constructed from acetylene-based scaffolds due its rigidity and linearity, allowing high exciton and electron coupling between chromophore units. Additionally, these systems are particularly important, considering the wide range of functional group interconversions that the triple bond may permit. This account represents a concise overview of the most important contributions on the synthesis and applications of mono- and poly-alkynyl-substituted phthalocyanine-based molecular systems, towards the development of new functional molecular materials.

Organic nanomaterials: synthesis, characterization, and device applications

Recent developments in nanoscience and nanotechnology have given rise to a new generation of functional organic nanomaterials with controlled morphology and well-defined properties, which enable a broad range of useful applications. This book explores some of the most important of these organic nanomaterials, describing how they are synthesized and characterized. Moreover, the book explains how researchers have incorporated organic nanomaterials into devices for real-world applications.