A 3-fold "butterfly valve" in command of the encapsulation's kinetic stability. Molecular baskets at work.

Molecular basket 1, composed of a semirigid tris-norbornadiene framework and three revolving pyridine-based gates at the rim, has been built to "dynamically" enclose space and as such regulate molecular encapsulation. The gates were shown to fold via intramolecular hydrogen bonding and thereby form a C3nu symmetrical receptor: the 1H NMR resonance for the amide N-H protons of the pyridine gates appeared downfield (delta= 10.98 ppm), and the N-H vibrational stretch (IR) was observed at 3176 cm(-1).

Molecular encapsulation via metal-to-ligand coordination in a Cu(I)-folded molecular basket.

A molecular basket, composed of a semirigid C3v symmetric tris-norbornadiene framework and three pyridine flaps at the rim, has been shown to coordinate to a Cu(I) cation and thereby fold in a multivalent fashion. The assembly was effective (Ka = 1.73 +/- 0.

Supramolecular catalysis at work: diastereoselective synthesis of a molecular bowl with dynamic inner space.

The supramolecular assistance to Pd(0)/Cu(I)-catalyzed cyclotrimerization of stannylated norbornene 7 has been investigated to give molecular bowl 1syn in a stereoselective fashion. Following a divergent strategy, racemic norbornene 7 was synthesized in satisfactory yield. Self-coupling, promoted by Pd(0)/Cu(I) catalysis acting in synergy with CsF, yielded molecular bowl 1syn in a moderate 30% yield.

Structure-function studies of modular aromatics that form molecular organogels.

Three urea-based aromatics 1-3, each with distinct steric and electronic characteristics, have been synthesized and their ability to undergo hierarchical assembly and gel organic solvents investigated. We have found that compound 1 promotes the sol-gel phase transition in primary alcohols (from CH3OH to C10H21OH; CGC < 15 mg/mL), while 2 and 3 do not. IR spectroscopy, X-ray powder diffraction (XRPD), and transmission electron microscopy (TEM) measurements show that 1 organizes into "cylinders" in primary alcohols, using three-centered hydrogen bonds and pi-pi aromatic interactions.

Silver(I) mediated folding of a molecular basket.

We have investigated Ag(I) mediated folding of a tridentate compound, containing three pyridine flaps tethered to a semirigid scaffold, into a molecular basket, using both experimental and theoretical methods. The basket formation has been shown to be highly favorable in organic media (Delta G degrees = -7.2 kcal/mol), with the assembly process allowing for another ligand to bind preferentially on the outer side.

Allosteric regulation of the conformational dynamics of a cavitand receptor.

[reaction: see text] Inspired by allostery in nature, we synthesized cavitand 1 and investigated regulation of its conformational dynamics. Quantitative 1H NMR studies have revealed that the rate of the conformational isomerization of 1 can be modulated using the external addition of acid. As 1 maintains its vase-like conformation in an acidic environment, ample opportunities for controlling the kinetics of molecular recognition, and thus reactivity, in this and related receptors have arisen.

Design, synthesis, and conformational dynamics of a gated molecular basket.

We have developed a synthesis and examined the conformational behavior and recognition properties of dynamic molecular containers 1-3. As follows from the 1H NMR dilution, diffusion NMR, and vapor pressure osmometry measurements, compound 1 has a low affinity for intermolecular aggregation and is mostly present in monomeric form in dilute chloroform solutions. Inspecting the O-H chemical shift resonances of 1, 3, and model compound 4 as a function of temperature afforded the deltadelta/deltaT coefficients of 17.