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Synfacts 2009(3): 0277-0277  
DOI: 10.1055/s-0028-1087763
Synthesis of Materials and Unnatural Products
© Georg Thieme Verlag Stuttgart ˙ New York

Endocyclic Modification to Porphyrinoid Tunes Energy Gap

Contributor(s): Timothy M. Swager, Jason R. Cox
M. Toganoh, T. Kimura, H. Uno, H. Furuta*
Kyushu University, Fukuoka and Ehime University, Matsuyama, Japan
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Publication History

Publication Date:
19 February 2009 (online)

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Significance

This paper reports the synthesis and electronic characterization of porphyrinoid 1. The doubly N-fused porphyrin was synthesized by acid-catalyzed [2+2] condensation followed by bromination and intramolecular cyclization. The resulting 18π compound displays an electronic absorption extending out to 1300 nm, which is characteristic of a 38π annulene. DFT calculations demonstrate that endocyclic carbon-nitrogen double bonds significantly raise the energy of the HOMO thus lowering the energy gap.