No abstract

With the advent of supramolecular chemistry and later nanotechnology a great deal of research has been focused on new types of molecular structures, which are not held together by covalent bonds but by non-covalent mechanical interactions. Examples include the catenane, rotaxane, and knot interlocked structures. The design and synthesis of these architectures is an art by itself and as such is worth being reviewed. In this tutorial review we will focus, however, on the functional aspects of interlocked molecules and discuss how these can find applications, e.g. as artificial muscles, as molecular valves, as components of electronic devices, and as catalysts.

N,N',N″-trialkylbenzene-1,3,5-tricarboxamides (BTAs) self-assemble by means of strong, threefold α-helix-type intermolecular hydrogen bonding into well-defined, helical, one-dimensional columnar aggregates. When a stereogenic centre is introduced into the alkyl side chains of these BTAs, strong Cotton effects are observed in dilute apolar solutions, indicating the preference for one helical conformation over the other. Here, we report the creation of a helical sense preference in self-assembled BTAs by introducing deuterium/hydrogen isotope chirality into the alkyl side chains. We determine the relative stabilities of the left- and right-handed helical conformations of these deuterated supramolecular polymers by performing a conformational analysis. Our findings show that the results of deuterium/hydrogen substitution in BTA-based supramolecular polymers and helical polyisocyanates are very similar, although the formation mechanisms differ. The selectively deuterated BTAs discussed here represent the first example of supramolecular chirality resulting from isotope substitution.

The amide bond is a versatile functional group and its directional hydrogen-bonding capabilities are widely applied in, for example, supramolecular chemistry. The potential of the thioamide bond, in contrast, is virtually unexplored as a structuring moiety in hydrogen-bonding-based self-assembling systems. We report herein the synthesis and characterisation of a new self-assembling motif comprising thioamides to induce directional hydrogen bonding. N,N',N''-Trialkylbenzene-1,3,5-tris(carbothioamide)s (thioBTAs) with either achiral or chiral side-chains have been readily obtained by treating their amide-based precursors with P2S5. The thioBTAs showed thermotropic liquid crystalline behaviour and a columnar mesophase was assigned. IR spectroscopy revealed that strong, three-fold, intermolecular hydrogen-bonding interactions stabilise the columnar structures. In apolar alkane solutions, thioBTAs self-assemble into one-dimensional, helical supramolecular polymers stabilised by three-fold hydrogen bonding. Concentration- and temperature-dependent self-assembly studies performed by using a combination of UV and CD spectroscopy demonstrated a cooperative supramolecular polymerisation mechanism and a strong amplification of supramolecular chirality. The high dipole moment of the thioamide bond in combination with the anisotropic shape of the resulting cylindrical aggregate gives rise to sufficiently strong depolarised light scattering to enable depolarised dynamic light scattering (DDLS) experiments in dilute alkane solution. The rotational and translational diffusion coefficients, D(trans) and D(rot), were obtained from the DDLS measurements, and the average length, L, and diameter, d, of the thioBTA aggregates were derived (L = 490 nm and d = 3.6 nm). These measured values are in good agreement with the value L(w) = 755 nm obtained from fitting the temperature-dependent CD data by using a recently developed equilibrium model. This experimental verification validates our common practice for determining the length of BTA-based supramolecular polymers from model fits to experimental CD data. The ability of thioamides to induce cooperative supramolecular polymerisation makes them effective and broadly applicable in supramolecular chemistry.

Small changes in the alkane solvent structure in combination with temperature effects lead to four different conformations of stereoselectively deuterated benzene-1,3,5-tricarboxamides in the aggregated state, affecting the expression of the supramolecular chirality and highlighting the role of the solvent structure in self-assembly processes.