Solvent-stabilized molecular capsules.
Pyrrogallolarenes 2 were prepared by acid-catalyzed condensation of pyrrogallol with aldehydes. Compound 2a crystallizes from a methanol solution of quinuclidine hydrochloride to give a dimeric molecular capsule surrounding one disordered quinuclidinium cation. The molecules of 2a are connected by direct hydrogen bonds and by bridging methanol and water molecules. The chloride anion is positioned outside the capsule and is hydrogen bonded to the hydroxy groups of 2a. The shortest distance between the cation and anion was found to be 6.7 A. Crystallization of 2b from aqueous acetonitrile resulted in a dimeric capsule linked by a polar belt of 16 hydrogen bonding water molecules. Four acetonitrile molecules occupy the cavity of this dimeric capsule and assume two binding sites that differ in hydrogen bonding and electronic environment. Compounds 2 also form hydrogen-bonded dimeric molecular capsules in alcohols and aqueous acetonitrile solutions. These assemblies readily encapsulate tetramethylammonium, tetramethylphosphonium, quinuclidinium, and tropylium cations to give complexes stable on the NMR time scale at 233 K.
Shivanyuk
Alexander
A
The Skaggs Institute for Chemical Biology and The Department of Chemistry, The Scripps Research Institute, MB-26, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Friese
Jan C
JC
Döring
Steve
S
Rebek
Julius
J
D002214:Capsules; D004355:Drug Stability; D000431:Ethanol / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D012996:Solutions; D012997:Solvents; D014961:X-Ray Diffraction
D002214:Capsules; D012996:Solutions; D012997:Solvents; D000431:Ethanol