Examining the Scope and Thermodynamics of Assembly in Nesting Complexes Comprising Molecular Baskets and TPA Ligands.

Molecular baskets capture various tris(2-pyridylmethyl)amine ligands, with and without zinc(II) cation, to form nesting complexes. The results of our computational (MD) and experimental (H NMR/ITC) studies suggest that the assembly is driven by the hydrophobic effect with the charge of complementary molecular components playing an important role in the formation of nesting complexes. In brief, the complexation only takes place when the basket and the ligand carry either oppositely charged or noncharged groups.

Anion-Redox Mechanism of MoO(S)(2,2'-bipyridine) for Electrocatalytic Hydrogen Production.

Redox processes of molybdenum-sulfide (Mo-S) compounds are important in the function of materials for various applications from electrocatalysts for the hydrogen evolution reaction (HER) to cathode materials for batteries. Our group has recently described a series of Mo-S molecular HER catalysts based on a MoO(S)L structural motif. Herein, reductive pathways of MoO(S)bpy (Mo-bpy) (bpy = 2,2'-bipyridine) are presented from both experimental and theoretical studies.

Assembly and Folding of Twisted Baskets in Organic Solvents.

A synthetic method for obtaining enantiopure and twisted baskets of type (P)-3 is described. These chiral cavitands were found to fold quinoline gates, at the rim of their twisted platform, in acetonitrile and give molecular capsules that assemble into large unilamellar vesicles. In a less polar dichloromethane, however, cup-shaped (P)-3 packed into vesicles but with the quinoline gates in an unfolded orientation.

Two-Dimensional Supramolecular Polymers Embodying Large Unilamellar Vesicles in Water.

We hereby describe a strategy for obtaining novel topological nanostructures consisting of dual-cavity basket 1, forming a curved monolayer of large unilamellar vesicles in water (CAC < 0.25 μM), and bivalent guests 4/5 populating the cavities of such bolaamphiphilic hosts. On the basis of the results of (1)H NMR spectroscopy, electron microscopy, and dynamic light scattering measurements, we postulated that divalent guest molecules 4/5 cover the curved vesicular surface in a lateral fashion to satisfy the complexation [2 + 2] valency and thereby give stable two-dimensional supramolecular polymers [1⊂4]n and [1⊂5]n.

Russian Nesting Doll Complexes of Molecular Baskets and Zinc Containing TPA Ligands.

In this study, we examined the structural and electronic complementarities of convex 1-Zn(II), comprising functionalized tris(2-pyridylmethyl)amine (TPA) ligand, and concave baskets 2 and 3, having glycine and (S)-alanine amino acids at the rim. With the assistance of (1)H NMR spectroscopy and mass spectrometry, we found that basket 2 would entrap 1-Zn(II) in water to give equimolar 1-Zn⊂2in complex (K = (2.0 ± 0.

Tunable Molecular MoS2 Edge-Site Mimics for Catalytic Hydrogen Production.

Molybdenum sulfides represent state-of-the-art, non-platinum electrocatalysts for the hydrogen evolution reaction (HER). According to the Sabatier principle, the hydrogen binding strength to the edge active sites should be neither too strong nor too weak. Therefore, it is of interest to develop a molecular motif that mimics the catalytic sites structurally and possesses tunable electronic properties that influence the hydrogen binding strength.

Dimeric [Mo2 S12 ](2-) Cluster: A Molecular Analogue of MoS2 Edges for Superior Hydrogen-Evolution Electrocatalysis.

Proton reduction is one of the most fundamental and important reactions in nature. MoS2 edges have been identified as the active sites for hydrogen evolution reaction (HER) electrocatalysis. Designing molecular mimics of MoS2 edge sites is an attractive strategy to understand the underlying catalytic mechanism of different edge sites and improve their activities.

Dual-cavity basket promotes encapsulation in water in an allosteric fashion.

We prepared dual-cavity basket 1 to carry six (S)-alanine residues at the entrance of its two juxtaposed cavities (289 Å(3)). With the assistance of (1)H NMR spectroscopy and calorimetry, we found that 1 could trap a single molecule of 4 (K1 = 1.45 ± 0.

Twisted baskets.

A preparative procedure for obtaining a pair of twisted molecular baskets, each comprising a chiral framework with either right ((P)-1syn) or left ((M)-1syn) sense of twist and six ester groups at the rim has been developed and optimized. The racemic (P/M)-1syn can be obtained in three synthetic steps from accessible starting materials. The resolution of (P/M)-1syn is accomplished by its transesterification with (1R,2S,5R)-(-)-menthol in the presence of a Ti(IV) catalyst to give diastereomeric 8(P) and 8(M).

Trapping of organophosphorus chemical nerve agents in water with amino acid functionalized baskets.

We prepared eleven amino-acid functionalized baskets and used (1) H NMR spectroscopy to quantify their affinity for entrapping dimethyl methylphosphonate (DMMP, 118 Å(3) ) in aqueous phosphate buffer at pH=7.0±0.1; note that DMMP guest is akin in size to chemical nerve agent sarin (132 Å(3) ).