Molecular Russian dolls

The host-guest recognition between two macrocycles to form hierarchical non-intertwined ring-in-ring assemblies remains an interesting and challenging target in noncovalent synthesis. Herein, we report the design and characterization of a box-in-box assembly on the basis of host-guest radical-pairing interactions between two rigid diradical dicationic cyclophanes. One striking feature of the box-in-box complex is its ability to host various 1,4-disubstituted benzene derivatives inside as a third component in the cavity of the smaller of the two diradical dicationic cyclophanes to produce hierarchical Russian doll like assemblies. These results highlight the utility of matching the dimensions of two different cyclophanes as an efficient approach for developing new hybrid supramolecular assemblies with radical-paired ring-in-ring complexes and smaller neutral guest molecules

Influence of Constitution and Charge on Radical Pairing Interactions in Tris-radical Tricationic Complexes

The results of a systematic investigation of trisradical tricationic complexes formed between cyclobis(paraquat-p-phenylene) bisradical dicationic (CBPQT2(•+)) rings and a series of 18 dumbbells, containing centrally located 4,4′-bipyridinium radical cationic (BIPY•+) units within oligomethylene chains terminated for the most part by charged 3,5-dimethylpyridinium (PY+) and/or neutral 3,5-dimethylphenyl (PH) groups, are reported. The complexes were obtained by treating equimolar amounts of the CBPQT4+ ring and the dumbbells containing BIPY2+ units with zinc dust in acetonitrile (MeCN) solutions. Whereas UV-VIS-NIR spectra revealed absorption bands centered on ca. 1100 nm with quite different intensities for the 1:1 complexes depending on the constitutions and charges on the dumbbells, titration experiments show that the association constants (Ka) for complex formation vary over a wide range from Ka values of 800 M^(-1) for the weakest to 180000 M^(-1) for the strongest. While Coulombic repulsions emanating from PY+ groups located at the ends of some of the dumbbells undoubtedly contribute to the destabilization of the trisradical tricationic complexes, solid-state superstructures support the contention that those dumbbells with neutral PH groups at the ends of flexible and appropriately constituted links to the BIPY•+ units stand to gain some additional stabilization from C‒H···π interactions between the CBPQT2(•+) rings and the PH termini on the dumbbells. The findings reported in this full paper demonstrate how structural changes implemented remotely from the BIPY•+ units influence their noncovalent bonding interactions with CBPQT2(•+) rings. Different secondary effects (Coulombic repulsions versus C‒H···π interactions) are uncovered and their contributions to both binding strengths associated with trisradical interactions and the kinetics of associations and dissociations are discussed at some length and are supported by extensive DFT calculations at the M06-D3 level. A fundamental understanding of molecular recognition in radical complexes has relevance when it comes to the design and synthesis of non-equilibrium systems

Molecular Russian dolls

The host-guest recognition between two macrocycles to form hierarchical non-intertwined ring-in-ring assemblies remains an interesting and challenging target in noncovalent synthesis. Herein, we report the design and characterization of a box-in-box assembly on the basis of host-guest radical-pairing interactions between two rigid diradical dicationic cyclophanes. One striking feature of the box-in-box complex is its ability to host various 1,4-disubstituted benzene derivatives inside as a third component in the cavity of the smaller of the two diradical dicationic cyclophanes to produce hierarchical Russian doll like assemblies. These results highlight the utility of matching the dimensions of two different cyclophanes as an efficient approach for developing new hybrid supramolecular assemblies with radical-paired ring-in-ring complexes and smaller neutral guest molecules

Controlling association kinetics in the formation of donor-acceptor pseudorotaxanes

We report a systematic investigation of size-complementary stoppering groups used to determine the kinetics of threading a cyclophane, namely cyclobis(paraquat-p-phenylene), onto a series of molecular dumbbells. We have identified a set of simple functionalized phenyl and biaryl groups that present activation energy barriers between 16.7 and 26.6 kcal mol(-1) to threading the dumbbells. These barriers will be employed as 'steric speed bumps' to modulate kinetics in artificial molecular pumps that operate based upon a delicate balance of noncovalent bonding interactions

Redox switchable daisy chain rotaxanes driven by radical-radical interactions

We report the one-pot synthesis and electrochemical switching mechanism of a family of electrochemically bistable 'daisy chain' rotaxane switches based on a derivative of the so-called 'blue box' (BB4+) tetracationic cyclophane cyclobis(paraquat-p-phenylene). These mechanically interlocked molecules are prepared by stoppering kinetically the solution-state assemblies of a self-complementary monomer comprising a BB4+ ring appended with viologen (V2+) and 1,5-dioxynaphthalene (DNP) recognition units using click chemistry. Six daisy chains are isolated from a single reaction: two monomers (which are not formally 'chains'), two dimers, and two trimers, each pair of which contains a cyclic and an acyclic isomer. The products have been characterized in detail by high-field H-1 NMR spectroscopy in CD3CN-made possible in large part by the high symmetry of the novel BB4+ functionality and the energies associated with certain aspects of their dynamics in solution are quantified. Cyclic voltammetry and spectroelectrochemistry have been used to elucidate the electrochemical switching mechanism of the major cyclic daisy chain products, which relies on spin-pairing interactions between V center dot+ and BB2(center dot+) radical cations under reductive conditions. These daisy chains are of particular interest as electrochemically addressable molecular switches because, in contrast with more conventional bistable catenanes and rotaxanes, the mechanical movement of the ring between recognition units is accompanied by significant changes in molecular dimensions. Whereas the self-complexed cyclic monomer known as a [cl]daisy chain or molecular 'ouroboros'-conveys sphincter-like constriction and dilation of its ultramacrocyclic cavity, the cyclic dimer ([c2]daisy chain) expresses muscle-like contraction and expansion along its molecular length