Polyphosphorylated Triphenylenes: Synthesis, Crystal Structure, and Selective Catechol Recognition

• Published in: Journal of organic chemistry 2009-01, Vol.74 (2), p.652-659
• Main Authors: Givelet, Cécile, Tinant, Bernard, Van Meervelt, Luc, Buffeteau, Thierry, Marchand-Geneste, Nathalie, Bibal, Brigitte
• Format: Article
• Language: English
• Subjects: Chemistry; Condensed benzenic and aromatic compounds; Exact sciences and technology; Noncondensed benzenic compounds; Organic chemistry; Preparations and properties
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo802015k

Designed as a multivalent hydrogen bond acceptor, new receptors, Discopus 1a,b, were built from a triphenylene core surrounded by six (diaryl)phosphinate groups. An efficient synthesis was developed to prepare these elaborated structures in a high overall yield. The X-ray structure of receptor 1b showed strong cooperative hydrogen bonds with two water molecules and intermolecular CH−π contacts. In chloroform, Discopus 1a,b displayed recognition properties toward dihydroxybenzenes, selectively forming complexes with catechol derivatives 4a−c in a 1:2 (host:guest) stoichiometry. According to NMR and microcalorimetry titrations, association constants were found in the 30−2837 M−1 range, which were larger than those reported for curvated catechol receptors (14−120 M−1). Interestingly, Discopus present two distinct catechol binding sites. Weak hydrogen bonding between host phosphinates and guest hydroxyl groups was shown by infrared spectroscopy and 31P NMR. Molecular dynamics simulations and recognition experiments suggested that a stronger hydrogen bond assisted by a π-interaction between the Discopus core and one catechol molecule could exist within the 1:2 complex.