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A voyage into the synthesis and photophysics of homo- and heterobinuclear ensembles of phthalocyanines and porphyrins.

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.