The remarkable properties of both phthalocyanines and porphyrins as individual building blocks have motivated the synthesis and study of homo- and heterobinuclear conjugates as light-harvesting systems. These planar chromophores share important electronic features such as high molar absorption coefficients, rich redox chemistry and interesting photoinduced energy and/or electron transfer abilities. In addition, some of these properties can be tuned by the introduction of different peripheral substituents and metal centres. In this review, we present relevant synthetic strategies for the preparation of covalent and supramolecular, homo- and heterobinuclear systems based on phthalocyanine and porphyrin chromophores, leading to a variety of architectures. In such systems, the degree of electronic interaction between the components is highly dependent on the electronic features of the two macrocycles, their linkage, and the molecular topology of the ensemble. In addition, incorporation of electroactive units into these binuclear systems has been pursued, affording multicomponent, donor-acceptor conjugates. In-depth photophysical characterization of the ground- and excited-state features of many of these homo- and heterobinuclear phthalocyanine and/or porphyrin ensembles has also been presented. Particular attention has been paid to understand the fundamental dynamics of the energy transfer and charge separation processes of these systems. This review intends to offer a general overview of the preparation of this class of compounds and the study of their photophysical properties which clearly show their potentiality as model compounds of light-harvesting complexes.

A 1,1,4,4-tetracyanobuta-1,3-diene (TCBD)-aniline moiety has been introduced, for the first time, at the axial position of two subphthalocyanines (SubPcs) peripherally substituted with hydrogen (HSubPc) or fluorine atoms (FSubPc). Single-crystal X-ray analysis of both SubPc-TCBD-aniline systems showed that each conjugate is a racemic mixture of two atropisomers resulting from the almost orthogonal geometry adopted by the axial TCBD unit, which were separated by chiral high-performance liquid chromatography. Remarkably, the single-crystal X-ray structure of one atropisomer of each SubPc-TCBD-aniline conjugate has been solved, allowing to unambiguously assign the atropisomers' absolute configuration, something, to the best of our knowledge, unprecedented in TCBD-based conjugates. Moreover, the physicochemical properties of both SubPc-TCBD-aniline racemates have been investigated using a wide range of electrochemical as well as steady-state and time-resolved spectroscopic techniques. Each of the two SubPc-TCBD-aniline conjugates presents a unique photophysical feature never observed before in SubPc chemistry. As a matter of fact, HSubPc-TCBD-aniline showed significant ground-state charge transfer interactions between the HSubPc macrocycle and the electron-withdrawing TCBD unit directly attached at its axial position. In contrast, FSubPc-TCBD-aniline gave rise to an intense, broad emission, which red shifts upon increasing the solvent polarity and stems from an excited complex (i.e., an exciplex). Such an exciplex emission, which has also no precedent in TCBD chemistry, results from intramolecular interactions in the excited state between the electron-rich aniline and the FSubPc π-surface, two molecular fragments kept in spatial proximity by the "unique" three-dimensional geometry adopted by the FSubPc-TCBD-aniline. Complementary transient absorption studies were carried out on both SubPc-TCBD-aniline derivatives, showing the occurrence, in both cases, of photoinduced charge separation and corroborating the formation of the aforementioned intramolecular exciplex in terms of a radical ion pair stabilized through-space.

In this review, we survey the role of carbon-based nanomaterials in energy-conversion schemes. In particular, we highlight charge-transfer processes on the molecular scale in sp 2 carbon in zero dimensions (fullerenes), sp 2 carbon in one dimension (carbon nanotubes), sp 2 carbon in two dimensions (graphene), and sp 2 /sp 3 carbon in zero and two dimensions (defectuous carbon nanostructures). As such, we conclude that the versatility of carbon-based nanomaterials in terms of structural and electronic properties renders them broadly applicable electroactive components for future energy devices.

The past 25 years have served as a test bed for exploring the chemistry and physics, in general, and the electron transfer chemistry, in particular, of low-dimensional carbon. Nevertheless, the new realm started with the advent of fullerenes, followed in chronological order by carbon nanotubes, and, more recently, by graphene. The major thrust of this Review article is to historically recap the versatility of fullerenes regarding the design, the synthesis, and the tests as an electroactive building block in photosynthetic reaction mimics, photovoltaics, and catalysis.

Monolayers and multilayers of cobalt octaethylporphyrin (CoOEP), cobalt tetraphenylporphyrin (CoTPP) and the corresponding free-base porphyrins 2HOEP and 2HTPP on an Au(111) surface were investigated with X-ray and UV photoelectron spectroscopy (XPS and UPS). For CoTPP and CoOEP monolayers, the XP spectra show a characteristic splitting of the Co 2p(3/2) signal, which suggests that only a fraction of the Co ions forms coordinative bonds to the Au(111) surface, while the others interact more weakly. This is a remarkable difference to previous results for CoOEP and CoTPP on Ag(111), where all Co ions in the monolayer were found to interact strongly and uniformly with the silver surface. Presumably, the lateral structural and electronic inhomogeneities of the reconstructed Au(111) surface are responsible for the more complex interaction behaviour on the gold surface. UP spectra of CoOEP and CoTPP monolayers show a new electronic state around 0.3 eV below the Fermi energy (E(F)), i.e., at lower binding energy than in the case of Ag(111), where a strong signal appeared at 0.6 eV below E(F). In contrast, the free-base porphyrins 2HOEP and 2HTPP show no additional valence states in the monolayer, indicating that the Co ion plays a central role in the electronic interaction between the metal complexes and the substrate. These results have important implications for metal/organic interfaces in organic electronics or photovoltaic devices based on pi-conjugated semiconducting metal complexes, because the character of the chemical bond at the interface determines important parameters such as charge injecting rates.

A cycloaddition-retroelectrocyclization reaction between tetracyanoethylene and two zinc phthalocyanines (Zn(II) Pcs) bearing one or four anilino-substituted alkynes has been used to install a strong, electron-accepting tetracyanobuta-1,3-diene (TCBD) between the electron-rich Zn(II) Pc and aniline moieties. A combination of photophysical, electrochemical, and spectroelectrochemical investigations with the Zn(II) Pc-TCBD-aniline conjugates, which present panchromatic absorptions in the visible region extending all the way to the near infrared, show that the formal replacement of the triple bond by TCBD has a dramatic effect on their ground- and excited-state features. In particular, the formation of extremely intense, ground-state charge-transfer interactions between Zn(II) Pc and the electron-accepting TCBD were observed, something unprecedented not only in Pc chemistry but also in TCBD-based porphyrinoid systems.

We report on a comprehensive transient absorption study with β,β'-linked bis[tetraphenylporphyrinato-zinc(II)] and its corresponding monomer, covering the ultrafast dynamics from femtoseconds up to several microseconds. By exciting these porphyrins either to their first (S(1)) or second (S(2)) electronically excited states and by probing the subsequent dynamics, a multitude of reaction pathways have been identified. In the spectral region associated with the ground-state recovery of the bisporphyrin, transient absorption changes occur within the first few picoseconds, which are ascribable to excitonic interaction both in the S(2) (fs time-domain) and in the S(1) (ps time-domain) state. This is substantiated by complementary experiments with the monomeric porphyrin, in which the S(2) state exhibits a longer lifetime. In contrast to the picosecond dynamics the bisporphyrin and the monomer behave similarly on the nanosecond time-scale, that is nearly all excited molecules eventually reach a long-lived triplet excited state.

A “frozen” electron donor–acceptor array that bears porphyrin and fullerene units covalently linked through the ortho position of a phenyl ring and the nitrogen of a pyrrolidine ring, respectively, is reported. Electrochemical and photophysical features suggest that the chosen linkage supports both through‐space and through‐bond interactions. In particular, it has been found that the porphyrin singlet excited state decays within a few picoseconds by means of a photoinduced electron transfer to give the rapid formation of a long‐lived charge‐separated state. Density functional theory (DFT) calculations show HOMO and LUMO to be localized on the electron‐donating porphyrin and the electron‐accepting fullerene moiety, respectively, at this level of theory. More specifically, semiempirical molecular orbital (MO) configuration interaction (CI) and unrestricted natural orbital (UNO)‐CI methods shed light on the nature of the charge‐transfer states and emphasize the importance of the close proximity of donor and acceptor for effective electron transfer.