Template-Directed Synthesis of Mechanically Interlocked Molecular Bundles Using Dynamic Covalent Chemistry

Mixing the dipyrido[24]crown-8 derivatives carrying one or two formyl group(s) on the 4 position(s) of their pyridine ring(s) with a 3-fold symmetrical trisammonium ion template in a 3:1 ratio in CD3NO2 results in the formation of thermodynamically stable [4]pseudorotaxanes which, upon addition of a 1,3,5 trisaminobenzene cap, form mechanically interlocked molecular bundles with one and two caps, respectively, by virtue of dynamic imine bond formation

Closed Aromatic Tubes-Capsularenes

In this study, we describe a synthetic method for incorporating arenes into closed tubes that we name capsularenes. First, we prepared vase-shaped molecular baskets 4–7. The baskets comprise a benzene base fused to three bicycle[2.2.1]heptane rings that extend into phthalimide (4), naphthalimide (6), and anthraceneimide sides (7), each carrying a dimethoxyethane acetal group. In the presence of catalytic trifluoroacetic acid (TFA), the acetals at top of 4, 6 and 7 change into aliphatic aldehydes followed by their intramolecular cyclization into 1,3,5-trioxane (1H NMR spectroscopy). Such ring closure is nearly a quantitative process that furnishes differently sized capsularenes 1 (0.7×0.9 nm), 8 (0.7×1.1 nm;) and 9 (0.7×1.4 nm;) characterized by X-Ray crystallography, microcrystal electron diffraction, UV/Vis, fluorescence, cyclic voltammetry, and thermogravimetry. With exceptional rigidity, unique topology, great thermal stability, and perhaps tuneable optoelectronic characteristics, capsularenes hold promise for the construction of novel organic electronic devices

Dynamic and Assembly Characteristics of Deep-Cavity Basket Acting as a Host for Inclusion Complexation of Mitoxantrone in Biotic and Abiotic Systems

We describe the preparation, dynamic, assembly characteristics of vase-shaped basket 13− along with its ability to form an inclusion complex with anticancer drug mitoxantrone in abiotic and biotic systems. This novel cavitand has a deep nonpolar pocket consisting of three naphthalimide sides fused to a bicyclic platform at the bottom while carrying polar glycines at the top. The results of 1H Nuclear Magnetic Resonance (NMR), 1H NMR Chemical Exchange Saturation Transfer (CEST), Calorimetry, Hybrid Replica Exchange Molecular Dynamics (REMD), and Microcrystal Electron Diffraction (MicroED) measurements are in line with 1 forming dimer [12]6−, to be in equilibrium with monomers 1(R)3− (relaxed) and 1(S)3− (squeezed). Through simultaneous line-shape analysis of 1H NMR data, kinetic and thermodynamic parameters characterizing these equilibria were quantified. Basket 1(R)3− includes anticancer drug mitoxantrone (MTO2+) in its pocket to give stable binary complex [MTO⊂1]− (Kd=2.1 μM) that can be precipitated in vitro with UV light or pH as stimuli. Both in vitro and in vivo studies showed that the basket is nontoxic, while at a higher proportion with respect to MTO it reduced its cytotoxicity in vitro. With well-characterized internal dynamics and dimerization, the ability to include mitoxantrone, and biocompatibility, the stage is set to develop sequestering agents from deep-cavity baskets

A Molecular Elevator

We report the incrementally staged design, synthesis, characterization and operation of a molecular machine that behaves like a nanoscale elevator. The operation of this device, which is made of a platform-like component interlocked with a trifurcated rig-like component and is only 3.5 by 2.5 nanometers in size, relies on the integration of several structural and functional molecular subunits. This molecular elevator is considerably more complex and better organized than previously reported artificial molecular machines. It exhibits a clear-cut on/off reversible behavior and it could develop forces up to around 200 piconewtons

Templated Synthesis of Interlocked Molecules

Mechanically interlocked molecular compounds can be synthesized in high yields by using template-directed assistance to covalent synthesis.Catenanes and rotaxanes are two classes of mechanically interlocked molecules that have been prepared using a variety of methods such as “clipping”,“slipping”, and “threading-followed-by-stoppering”,under both kinetic and thermodynamic regimes. These different methods have utilized a range of templates such as transistion metals, p-donor/p-acceptors, and hydrogen-bonding motifs. Multivalency has emerged as another tool to aid and abet the supramolecularly assisted synthesis of mechanically interlocked molecules. Recent advances in our understanding of the nature of the mechanical bond has led to the construction of molecular machines with controllable motions that have, in one instance, been introduced into molecular electronic devices