Modular synthesis of π-acceptor cyclophanes derived from 1,4,5,8-naphthalenetetracarboxylic diimide and 1,5-dinitronaphthalene

Three neutral cyclophanes were synthesized, and their association with indole, an aromatic π-donor, was studied. The cyclophanes were designed to contain a rigid, hydrophobic binding cavity with 1,4,5,8-naphthalenetetracarboxylic diimide or 1,5-dinitronaphthalene as the π-acceptor. Two of the cyclophanes also contain a (S)-(valine-leucine-alanine) tripeptide unit to provide chiral hydrogen bonding interactions with guest molecules. Despite the fact that these cyclophanes contain a hydrophobic binding cavity of appropriate dimensions, their association with indole is very weak. In the case of cyclophanes derived from 1,5-dinitronaphthalene, steric interactions force the nitro groups out of the plane of the naphthalene ring, diminishing their effectiveness as π-acceptors. A simple UV-visible titrimetric method, using N,N,N′,N′-tetramethyl-1,4-phenylenediamine (TMPD) as a π-donor, was used to rank the π-acceptor strength of these and other aromatic units. These titrations show that 1,4,5,8-naphthalenetetracarboxylic diimide and 1,5-dinitronaphthalene derivatives are weaker π-acceptors than viologens, which make good π-acceptor cyclophanes. Methyl viologen is in turn a weaker π-acceptor than anthaquinone disulfonate, suggesting that the latter may serve as a useful building block for π-accepting cyclophane hosts.