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Porphycenes, the first structural isomer of porphyrin, display unique chemical and photophysical properties. In this Account , we detail our group's individual and collaborative efforts in elucidating further the chemical properties of porphycene. Particular emphasis will be placed on recent efforts devoted to expanding the porphycene core. 1 Introduction 2 Exploring the Chemistry of Porphycene 3 Synthesis and Metalation of an Expanded Porphycene 4 Conclusion [ABSTRACT FROM AUTHOR]

Abstract: A new expanded porphycene with 26 π‐electrons has been prepared by the McMurry coupling of 1,4‐bis(3,4‐diethyl‐2‐pyrryl)benzene dialdehyde. Expansion of the porphycene framework provides a ligand capable of stabilizing a bis(rhodium) and a monoruthenium complex. These new porphycene derivatives absorb strongly in the NIR spectral region, with appreciable absorptivity up to 1300 nm. On the basis of their ground‐ and excited‐state spectroscopic features and structural parameters, both the free‐base system and the bis(rhodium) complex are considered to be Hückel‐type aromatic systems. This conclusion is supported by DFT calculations. [ABSTRACT FROM AUTHOR]