Nitrogen Heterocyclic Carbon-Rich Materials:  Synthesis and Spectroscopic Properties of Dehydropyridoannulene Macrocycles

• Published in: Journal of organic chemistry 2005-06, Vol.70 (13), p.4935-4953
• Main Authors: Baxter, Paul N. W, Dali-Youcef, Riad
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Organic chemistry; Preparations and properties
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo040276f

A new series of nitrogen heterocyclic dehydroannulenes 1−3 have been synthesized and their macrocyclic structures assigned using spectroscopic methods. The chiral and planar ground state conformations of 1 and 3, respectively, were determined by semiempirical theoretical calculations. All dehydropyridoannulenes and precursors possessing four aromatic rings functioned as fluorescent chromophores. A detailed spectroscopic investigation into the cation-binding properties of 3 in dilute solution revealed a particularly selective photoluminescence quenching sensory response for PdII ions. Cycle 3, as well as 1 and 2, also exhibited reversible proton-triggered luminescence quenching behavior. At higher concentrations, 3 afforded a coordination polymer precipitate with AgI ions. Cycles 1 and 2 and precursors 15, 23, and 29 also undergo thermochemical reactions that may potentially lead to carbon-rich polymers. The physicochemical properties of 1−3 suggest that dehydropyridoannulenes may serve as a particularly versatile new class of ligands for the creation of novel heteroatom-containing carbon-rich materials with many potential applications in supramolecular materials science and nanotechnology.