Polyamide–polyamine hybrid macrobicycle L is explored with respect to its ability to bind α,ω-dicarboxylate anions. Potentiometric studies of protonated L with the series of dianions from succinate (suc2–) through glutarate (glu2–), α-ketoglutarate (kglu2–), adipate (adi2–), pimelate (pim2–), suberate (sub2–), to azelate (aze2–) have shown adipate preference with association constant value of K = 4900 M–1 in a H2O/DMSO (50:50 v/v) binary solvent mixture. The binding constant increases from glu2– to adi2– and then continuously decreases with the length of the anion chain. Further, potentiometric studies suggest that hydrogen bonding between the guest anions and the amide/ammonium protons of the receptor also contributes to the stability of the associations along with electrostatic interactions. Negative-mode electrospray ionization of aqueous solutions of host–guest complexes shows clear evidence for the selective formation of 1:1 complexes. Single-crystal X-ray structures of complexes of the receptor with glutaric acid, α-ketoglutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid assist to understand the observed binding preferences. The solid-state structures reveal a size/shape complementarity between the host and the dicarboxylate anions, which is nicely reflected in the solution state binding studies.

The self-sorting processes in dynamic libraries of cucurbit[8]uril complexes can be switched in an orthogonal way by external stimuli. Protonated phenylpyridine guests form a 2 : 1 homoternary π-donor–π-acceptor complex, while deprotonation makes it a partner for ethylviologen in a 1 : 1 : 1 heteroternary complex. Reduction of the viologen instead generates a 2 : 1 homoternary complex of viologen radical-cations.

Two new Zn4L6 cages composed of diamine subcomponents containing either naphthalene diimide (NDI) or porphyrin moieties are described. Their structural differences allow these cages to exhibit distinct interactions with different chemical stimuli, yielding different supramolecular products. The electron-poor NDI subunits of the first cage were observed to thread through electron-rich aromatic crown-ether macrocycles, forming mechanically-interlocked species up to a [3]catenane, whereas the porphyrin ligands of the second cage interacted favourably with C70, causing it to be bound as a guest. When mixed, the two cages were observed to form a dynamic combinatorial library (DCL) of seven constitutionally distinct mixed-ligand Zn4L6 cages. The DCL was observed to reconstitute in opposing ways when treated with either the crown ether or C70: the electron-rich macrocycle templated the formation of heteroleptic catenanes, whereas C70 caused the DCL to self-sort into homoleptic structures.

Antimonato polyoxovanadate (POV) cluster compounds {M(en)3}3[V15Sb6O42(H2O)x]·nH2O (M = FeII, CoII, NiII and x = 0 or 1) obtained under solvothermal conditions exhibit unusual high water solubility making these compounds promising synthons for generation of new POV structure types. Electrospray ionization mass spectrometry provides evidence (i) for a water molecule encapsulated inside the cavity of a fraction of the spherical cluster shells, (ii) for a post-functionalization in water, namely a slow exchange of VO against Sb2O, (iii) for the inner-phase reactivity of the encapsulated water that is capable of opening an oxo-bridge, and (iv) for a significant acceleration of the 16O/18O exchange reactions of oxygen atoms in the cluster periphery with surrounding H218O, when encapsulated water is present. To the best of our knowledge, this is the first example in polyoxovanadate chemistry for the transduction of inner-phase reactivity of an encapsulated guest molecule into changes in the outer-phase reactivity of the cluster. Magnetic susceptibility measurements reflect the individual contributions of the frustrated {V15} spin polytope and the {M(en)3}2+ complexes, with very weak coupling between these groups.

Lower critical solution temperature (LCST) phase behaviour of an imidazolium-based ionic liquid is reported, which can be controlled by concentration, the choice of cation, anion and solvent, and by supramolecular host–guest complex formation. Molecular dynamics simulations provide insight into the molecular basis of this LCST phenomenon. This thermo-responsive system has potential applications in cloud point extraction processes.

A pillar[5]arene-based bioactive guest loading system has been developed, which can increase the solubility of the drug norharmane in aqueous medium, and also enable its pH-stimulated release. Furthermore, this supramolecular transport system reduces the toxicity of loaded guest.

A novel linear hybrid tris-bidentate neutral ligand having 2,2′-bipyridine and two terminal triazolylpyridine coordination sites (L) was efficiently synthesized and explored in the synthesis of trinuclear triple-stranded homometallic side-by-side helicates L3Fe3(OTf)6 (1) and L3Zn3(OTf)6 (2), in which the three metal centers display alternating Λ and Δ configurations. Selective formation of the analogous heterometallic side-by-side helicate L3Fe2Zn(OTf)6 (3) was achieved from a mixture of L, Fe(CH3CN)2(OTf)2, and Zn(OTf)2 (1:1:1) in acetonitrile at room temperature. Various analytical techniques, i.e., single-crystal X-ray diffraction and NMR and UV/vis spectroscopy, were used to elucidate the sequence of the metal atoms within the heterometallic helicate, with the Zn2+ at the central position. The formation of 3 was also achieved starting from either L3Zn3(OTf)6 or L3Fe3(OTf)6 by adding Fe(CH3CN)2(OTf)2 or Zn(OTf)2, respectively. ESI-MS and 1H NMR studies elucidated different transmetalation mechanisms for the two cases: While a Zn2+-to-Fe2+ transmetalation occurs by the stepwise exchange of single ions on the helicate L3Zn3(OTf)6 at room temperature, this mechanism is almost inoperative for the Fe2+-to-Zn2+ transmetalation in L3Fe3(OTf)6, which is kinetically trapped at room temperature. In contrast, dissociation of L3Fe3(OTf)6 at higher temperature is required, followed by reassembly to give L3Fe2Zn(OTf)6. The reassembly follows an interesting mechanistic pathway when an excess of Zn(OTf)2 is present in solution: First, L3Zn3(OTf)6 forms as the high-temperature thermodynamic product, which is then slowly converted into the thermodynamic heterometallic L3Fe2Zn(OTf)6 product at room temperature. The temperature-dependent equilibrium shift is traced back to significant entropy differences resulting from an enhancement of the thermal motion of the ligands at high temperature, which destabilize the octahedral iron terminal complex and select zinc in a more stable tetrahedral geometry.

The formation of singly, doubly and triply threaded pseudo[2]rotaxanes with diketopiperazine threads and tetralactam wheels is investigated with respect to chelate cooperativity effects on multivalent binding. Two series of guest molecules are prepared which differ with respect to their spacers, one with preorganised centrepieces with di- or tripodal roof-like structures, one with more flexible spacers. The thermodynamics of pseudorotaxane formation is examined using isothermal titration calorimetry and 1H NMR spectroscopy. Force-field calculations provide more detailed structural insight and help rationalizing the thermodynamic data. All di- and trivalent pseudorotaxanes exhibit positive chelate cooperativity presumably arising from spacer–spacer interactions. Higher cooperativity factors are observed for the more preorganised threads.

In this Account, the recent progress in the construction of functional macrocycle-containing supramolecular gels is summarized. First, recent strategies to engineer responsiveness into macrocycle-containing gels are discussed. Next, different functions are presented including applications as responsive reaction media, for controlled drug-delivery or tissue engineering, and as self-healing materials. Finally, we highlight the recent progress in designing macrocycle-containing supramolecular gel materials exhibiting complex behavior. This field is part of systems chemistry and still in its infancy but appears to be one of the most promising routes to smart responsive materials.

In order to investigate molecular recognition on surfaces, an azide-functionalized monolayer was deposited on gold. The monolayer was characterized by X-ray photoelectron spectroscopy (XPS) and angle-resolved near-edge X-ray absorption fine structure (NEXAFS) experiments and the decomposition of the azide upon irradiation with X-ray beams was investigated. Subsequently, various alkyne-functionalized host and guest molecules were attached to the azide by 1,3-dipolar cycloaddition. These modified surfaces and their host–guest chemistry were analysed by XPS and angle-resolved NEXAFS. The reversibility of guest binding was shown for one example as a proof of principle.

A detailed thermodynamic analysis of the axle-wheel binding in di- and trivalent secondary ammonium/[24]crown-8 pseudorotaxanes is presented. Isothermal titration calorimetry (ITC) data and double mutant cycle analyses reveal an interesting interplay of positive as well as negative allosteric and positive chelate cooperativity thus providing profound insight into the effects governing multivalent binding in these pseudorotaxanes.

Two new Zn4L6 cages composed of diamine subcomponents containing either naphthalene diimide (NDI) or porphyrin moieties are described. Their structural differences allow these cages to exhibit distinct interactions with different chemical stimuli, yielding different supramolecular products. The electron-poor NDI subunits of the first cage were observed to thread through electron-rich aromatic crown-ether macrocycles, forming mechanically-interlocked species up to a [3]catenane, whereas the porphyrin ligands of the second cage interacted favourably with C70, causing it to be bound as a guest. When mixed, the two cages were observed to form a dynamic combinatorial library (DCL) of seven constitutionally distinct mixed-ligand Zn4L6 cages. The DCL was observed to reconstitute in opposing ways when treated with either the crown ether or C70: the electron-rich macrocycle templated the formation of heteroleptic catenanes, whereas C70 caused the DCL to self-sort into homoleptic structures.

A novel photoswitchable rotaxane was synthesised and its switching behaviour in solution was analysed with NMR and UV-Vis. A monolayer of rotaxanes was deposited on glass surfaces and the on-surface photoswitching was investigated. Angle-resolved NEXAFS spectra revealed a preferential orientation that reversibly changes upon switching.

Mono-, di- and trivalent pseudorotaxanes with tetralactam macrocycle hosts and axles containing diamide binding stations as the guests have been synthesised. Their threading behaviour was analyzed in detail by NMR experiments and isothermal titration calorimetry. An X-ray crystal structure of the monovalent pseudorotaxane confirms the binding motif. Double mutant cycle analysis provides the effective molarities and insight into the chelate cooperativity of multivalent binding. While the second binding event in a trivalent pseudorotaxane exhibits a slightly positive cooperativity, the third binding is nearly non-cooperative. Nevertheless, the enhanced binding affinities resulting from the multivalent interaction are the basis for a highly efficient synthesis of di- and trivalent rotaxanes through stoppering the axle termini by “click” chemistry. Evidence for the multiply threaded geometry comes from NMR spectroscopy as well as tandem mass-spectrometric fragmentation experiments of mass-selected rotaxane ions in the gas phase. Furthermore, the trivalent rotaxane can be controlled by external stimuli (chloride addition and removal) which lead to an elevator-type movement of the wheel along the axle.

Four monomeric building blocks equipped with one crown ether and one secondary ammonium ion are synthesized and studied with respect to their ability to form daisy chain dimers. Two crown ethers with different cavity sizes – i.e. [21]crown-7 and [24]crown-8 – and two ammonium ions substituted with either a thin alkyl group or a more bulky benzyl group are used as the binding motifs. Self-sorting behaviour can be expected as the [21]crown-7/alkyl ammonium and [24]crown-8/benzyl ammonium binding motifs are orthogonal. Three homodimers are characterized by NMR, X-ray crystallography and ESI mass spectrometry. They are recognizable by the presence of signals for diastereotopic protons in the 1H NMR spectra. The formation of hetero-[c2]daisy chain dimers can be monitored by NMR spectroscopy and ESI mass spectrometry and show the expected self-sorting behaviour.

A pillar[5]arene-based bioactive guest loading system has been developed, which can increase the solubility of the drug norharmane in aqueous medium, and also enable its pH-stimulated release. Furthermore, this supramolecular transport system reduces the toxicity of loaded guest.

Antimonato polyoxovanadate (POV) cluster compounds {M(en)3}3[V15Sb6O42(H2O)x]·nH2O (M = FeII, CoII, NiII and x = 0 or 1) obtained under solvothermal conditions exhibit unusual high water solubility making these compounds promising synthons for generation of new POV structure types. Electrospray ionization mass spectrometry provides evidence (i) for a water molecule encapsulated inside the cavity of a fraction of the spherical cluster shells, (ii) for a post-functionalization in water, namely a slow exchange of VO against Sb2O, (iii) for the inner-phase reactivity of the encapsulated water that is capable of opening an oxo-bridge, and (iv) for a significant acceleration of the 16O/18O exchange reactions of oxygen atoms in the cluster periphery with surrounding H218O, when encapsulated water is present. To the best of our knowledge, this is the first example in polyoxovanadate chemistry for the transduction of inner-phase reactivity of an encapsulated guest molecule into changes in the outer-phase reactivity of the cluster. Magnetic susceptibility measurements reflect the individual contributions of the frustrated {V15} spin polytope and the {M(en)3}2+ complexes, with very weak coupling between these groups.

The formation of singly, doubly and triply threaded pseudo[2]rotaxanes with diketopiperazine threads and tetralactam wheels is investigated with respect to chelate cooperativity effects on multivalent binding. Two series of guest molecules are prepared which differ with respect to their spacers, one with preorganised centrepieces with di- or tripodal roof-like structures, one with more flexible spacers. The thermodynamics of pseudorotaxane formation is examined using isothermal titration calorimetry and 1H NMR spectroscopy. Force-field calculations provide more detailed structural insight and help rationalizing the thermodynamic data. All di- and trivalent pseudorotaxanes exhibit positive chelate cooperativity presumably arising from spacer–spacer interactions. Higher cooperativity factors are observed for the more preorganised threads.

Lower critical solution temperature (LCST) phase behaviour of an imidazolium-based ionic liquid is reported, which can be controlled by concentration, the choice of cation, anion and solvent, and by supramolecular host–guest complex formation. Molecular dynamics simulations provide insight into the molecular basis of this LCST phenomenon. This thermo-responsive system has potential applications in cloud point extraction processes.