Henrik Löw

All‐carbon cages: In just three steps imine cages are converted into hydrocarbon cages by reduction, nitrosylation, and formation of the C−C bonds by an Overberger reaction. The method has been successfully applied to even larger structures, such as derivatives of C₇₂H₇₂.

Abstract

In contrast to organic cages which are formed by exploiting dynamic covalent chemistry, such as boronic ester cages, imine cages, or disulfide cages, those with a fully carbonaceous backbone are rarer. With the exception of alkyne metathesis based approaches, the vast majority of hydrocarbon cages need to be synthesized by kinetically controlled bond formation. This strategy implies a multiple step synthesis and no correction mechanism in the final macrocyclization step, both of which are responsible for low overall yields. Whereas for smaller cages the intrinsic drawbacks are not always obvious, larger cages are seldom synthesized in yields beyond a few tenths of a percent. Presented herein is a three‐step method to convert imine cages into hydrocarbon cages. The method has been successfully applied to even larger structures such as derivatives of C₇₂H₇₂ , an unknown cage suggested by Fritz Vögtle more than 20 years ago.

Homochiral domains appear in supramolecular assemblies formed by the achiral monomers 2,4,6‐triaminopyrimimidine and a modified cyanuric acid. These samples become uniformly homochiral when as little as 0.1 % of a chiral cyanuric acid monomer is added, or when there is at least a 6 % ee in samples containing both enantiomers of the chiral monomer.

Abstract

Aqueous solutions of the achiral, monomeric, nucleobase mimics (2,4,6‐triaminopyrimidine, TAP, and a cyanuric acid derivative, CyCo6) spontaneously assemble into macroscopic homochiral domains of supramolecular polymers. These assemblies exhibit a high degree of chiral amplification. Addition of a small quantity of one handedness of a chiral derivative of CyCo6 generates exclusively homochiral structures. This system exhibits the highest reported degree of chiral amplification for dynamic helical polymers or supramolecular helices. Significantly, homochiral polymers comprised of hexameric rosettes with structural features that resemble nucleic acids are formed from mixtures of cyanuric acid (Cy) and ribonucleotides (l‐, d‐pTARC) that arise spontaneously from the reaction of TAP with the sugars. These findings support the hypothesis that nucleic acid homochirality was a result of symmetry breaking at the supramolecular polymer level.

The synthesis of complex organic compounds is largely a manual process that is often incompletely documented. To address these shortcomings, we developed an abstraction that maps commonly reported methodological instructions into discrete steps amenable to automation. These unit operations were implemented in a modular robotic platform using a chemical programming language which formalizes and controls the assembly of the molecules. We validated the concept by directing the automated system to synthesize three pharmaceutical compounds, Nytol, rufinamide, and sildenafil, without any human intervention. Yields and purities of products and intermediates were comparable to or better than those achieved manually. The syntheses are captured as digital code that can be published, versioned, and transferred flexibly between platforms with no modification, thereby greatly enhancing reproducibility and reliable access to complex molecules.

Macroscopic helical chirality and self-motion of hierarchical self-assemblies induced by enantiomeric small molecules

Macroscopic helical chirality and self-motion of hierarchical self-assemblies induced by enantiomeric small molecules, Published online: 18 September 2018; doi:10.1038/s41467-018-06239-5

Chirality transfer by chemical self-assembly has been studied intensively for years but chirality transfers along the same path remains elusive. Here the authors use a multiscale chemo-mechanical model to elucidate the mechanism underlying the chirality transfer via self-assembly in hierarchical camphorsulfonic acid doped polyaniline.

Abstract

With the rise of artificial molecular machines, control of motion on the nanoscale has become a major contemporary research challenge. Tetrathiafulvalenes (TTFs) are one of the most versatile and widely used molecular redox switches to generate and control molecular motion. TTF can easily be implemented as functional unit into molecular and supramolecular structures and can be reversibly oxidized to a stable radical cation or dication. For over 20 years, TTFs have been key building blocks for the construction of redox-switchable mechanically interlocked molecules (MIMs) and their electrochemical operation has been thoroughly investigated. In this review, we provide an introduction into the field of TTF-based MIMs and their applications. A brief historical overview and a selection of important examples from the past until now are given. Furthermore, we will highlight our latest research on TTF-based rotaxanes.

Beilstein J. Org. Chem. 2018, 14, 2163–2185. doi:10.3762/bjoc.14.190

Angewandte Chemie International Edition, EarlyView.

Abstract

We introduce herein boron-dipyrromethene (BODIPY) dyes as a new class of fluorophores for the design of reporter dyes for supramolecular host–guest complex formation with cucurbit[7]uril (CB7). The BODIPYs contain a protonatable aniline nitrogen in the meso-position of the BODIPY chromophore, which was functionalized with known binding motifs for CB7. The unprotonated dyes show low fluorescence due to photoinduced electron transfer (PET), whereas the protonated dyes are highly fluorescent. Encapsulation of the binding motif inside CB7 positions the aniline nitrogen at the carbonyl rim of CB7, which affects the pK_a value, and leads to a host-induced protonation and thus to a fluorescence increase. The possibility to tune binding affinities and pK_a values is demonstrated and it is shown that, in combination with the beneficial photophysical properties of BODIPYs, several new applications of host–dye reporter pairs can be implemented. This includes indicator displacement assays with favourable absorption and emission wavelengths in the visible spectral region, fluorescence correlation spectroscopy, and noncovalent surface functionalization with fluorophores.

Beilstein J. Org. Chem. 2018, 14, 1961–1971. doi:10.3762/bjoc.14.171

Abstract

A two-station [2]catenane containing a large macrocycle with two different recognition sites, one bis(pyridinium)ethane and one benzylanilinium, as well as a smaller DB24C8 ring was synthesized and characterized. ¹H NMR spectroscopy showed that the DB24C8 ring can shuttle between the two recognition sites depending on the protonation state of the larger macrocycle. When the aniline group is neutral, the DB24C8 ring resides solely at the bis(pyridinium)ethane site, while addition of acid forms a charged benzylanilinium site. The DB24C8 then shuttles between the two charged recognition sites with occupancy favoring the bis(pyridinium)ethane site by a ratio of 4:1. The unprotonated [2]catenane has a deep yellow/orange color when the DB24C8 ring resides solely at the bis(pyridinium)ethane site and changes to colorless when the crown ether is shuttling (i.e., circumrotating) back and forth between the two recognition sites thus optically signalling the onset of the shuttling dynamics.

Beilstein J. Org. Chem. 2018, 14, 1908–1916. doi:10.3762/bjoc.14.165

Angewandte Chemie International Edition, EarlyView.

Chemistry – An Asian Journal, EarlyView.

Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors

Artificial muscle-like function from hierarchical supramolecular assembly of photoresponsive molecular motors, Published online: 04 December 2017; doi:10.1038/nchem.2887

A centimetre-long string formed by the hierarchical self-assembly of a photoresponsive amphiphilic molecular motor — composed of 95 wt% of water — undergoes muscle-like contraction. Under irradiation, rotary motion at the molecular level is amplified through non-covalent interactions to sustain a fast macroscopic mechanical motion of large amplitude.

Abstract

Abstract

Abstract

Nature Chemistry. doi:10.1038/nchem.2745

Authors: Yudong Hao, Martin Kristiansen, Ruojie Sha, Jens J. Birktoft, Carina Hernandez, Chengde Mao & Nadrian C. Seeman

Although DNA nanotechnology has found many applications in developing functional structures, there has never been an independent device contained within a 3D crystal. Now, a self-assembled three-state device that can change the colour of its crystal by diffusion of DNA-ligated dyes has been reported, representing the potential to develop programmable nanomechanical devices.