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.
Bibliographical noteFunding Information:
G.A. thanks the Fundación Ramón Areces (Madrid, Spain) for a postdoctoral fellowship. This work was supported by the National Science Foundation (grant CHE-1402004 to J.L.S.) and the Robert A. Welch Foundation (F-0018 to J.L.S.). The work at Yonsei University was supported by a National Research Foundation of Korea (NRF) grant funded by the Korean government (MEST; 2016R1E1A1A01943379). J.T.B. thanks the NSF for an EAPSI fellowship.
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