In irons bound: Linear diamine and formylpyridine subcomponents form a tetrahedral cage with iron(II) in water (see scheme). This traps hydrophobic guests high specificity within rigid cavity, isolating them from the aqueous environment. The may be broken, releasing guest, upon addition of triamine. It also unlocked by adding acid, allowing guest to reversibly released until base is added, relocking it within. Supporting information for this article available on WWW under...

Abstract Two [N⋅⋅⋅I + ⋅⋅⋅N] halogen‐bonded dimeric capsules using tetrakis(3‐pyridyl)ethylene cavitands with different lower rim alkyl chains are synthesized and analyzed in solution the gas phase. These first examples of symmetrical making use iodonium ion (I ) as main connecting module characterized by 1 H NMR spectroscopy, diffusion ordered spectroscopy (DOSY), electrospray ionization mass spectrometry (ESI‐MS), mobility‐mass (TW‐IMS) experiments. The synthesis effective dimerization...

Survival of the fittest: Only those hexameric pyrogallarene and resorcinarene capsules which contain a guest with right size, shape, symmetry (see picture) survive electrospray ionization process that makes them detectable by mass spectrometry. Tandem MS experiments mass-selected ions provide evidence hexamers retain their capsular structure even in gas phase.

Lineare Diamin- und Formylpyridin-Einheiten bilden mit Eisen(II) einen tetraedrischen Käfig (siehe Schema), der hydrophobe Gastspezies hoch spezifisch in seinem Hohlraum aufnimmt von wässrigen Umgebung abschirmt. Beim Öffnen des Käfigs durch Zusatz eines Triamins wird die eingeschlossene Spezies freigesetzt. Alternativ zerfällt bei Zugabe Säure, doch dieser Prozess kann Base rückgängig gemacht werden, sodass reversibel freigesetzt eingeschlossen wird.

Iodine (I2) acts as a bifunctional halogen-bond donor connecting two macrocyclic molecules of the bowl-shaped acceptor, N-cyclohexyl ammonium resorcinarene chloride 1, to form dimeric capsule [(1,4-dioxane)3@1(2)(I2)2]. The is constructed solely through halogen bonds and has single cavity (V=511 Å(3)) large enough encapsulate three 1,4-dioxane guest molecules.

Abstract Subtle differences in metal–ligand bond lengths between a series of [M 4 L 6 ] 4− tetrahedral cages, where M=Fe II , Co or Ni were observed to result substantial affinity for hydrophobic guests water. Changing the metal ion from iron(II) cobalt(II) nickel(II) increases size interior cavity cage and allows encapsulation larger guest molecules. NMR spectroscopy was used study recognition properties cages towards small water, single‐crystal X‐ray diffraction solid‐state complexes cages.

Pyrophosphate (PPi) is a byproduct of DNA and RNA synthesis, abnormal levels are indicative disease. We report the high-affinity binding PPi in water by N-alkyl ammonium resorcinarene chloride receptors. Experimental analysis using 1H 31P NMR, isothermal titration calorimetry, mass spectrometry, UV-vis spectroscopy all support exceptional selectivity these systems for water. The measured affinity K1 = 1.60 × 107 M-1 three orders magnitude larger than that observed to another phosphate, ATP....

Abstract The limited diversity in targets of available antibiotic therapies has put tremendous pressure on the treatment bacterial pathogens, where numerous resistance mechanisms that counteract their function are becoming increasingly prevalent. Here, we utilize an unconventional anti-virulence screen host-guest interacting macrocycles, and identify a water-soluble synthetic macrocycle, Pillar[5]arene, is non-bactericidal/bacteriostatic mechanism action involves binding to both homoserine...

Alternative to complex labelling of resorcinarene hosts with redox-active probes, noncovalent formation offers a unique avenue toward bifunctional hosts, which posses redox centers transduce an electrochemical signal as well maintaining guest recognition site. Herein, N-alkyl ammonium halides (NARXs) were evaluated well-known probe ferrocene (Fc). Specifically, the NARX designed based on tuning upper rim allow for hydrogen bonding, pi–pi stacking, ion and halogen binding interactions in...

Abstract The non‐covalent interactions of different upper‐rim‐substituted C 2 ‐resorcinarenes with tetramethylammonium salts were analyzed in the gas phase an Electrospray Ionization Fourier‐transform ion‐cyclotron‐resonance (ESI‐FTICR) mass spectrometer and by 1 H NMR titrations. order binding strengths hosts towards cation reflects electronic nature substituents on upper rim resorcinarene. In solution, however, a trend particularly high constants for halogenated resorcinarenes has been...

Cyclophanes are macrocyclic supramolecular hosts famous for their ability to bind atomic or molecular guests via noncovalent interactions within well-defined cavities. In a similar way, porous crystalline networks, such as metal–organic frameworks, can create microenvironments that enable controlled guest binding in the solid state. Both types of materials often consist synthetic components, and they have been developed separate research fields. Moreover, use biomolecules structural units...

The first examples of halogen bonded analogues deep cavity cavitands with guest binding properties, formed between N-alkyl ammonium resorcinarene halides as acceptors and bromotrichloromethane the donor, are reported in solid state solution.

Abstract Supramolecular chemistry research is focused on the study of weak non‐covalent intermolecular — that is, supramolecular interactions as driving force in self‐assembly and molecular recognition. Dimeric resorcin[4]arenes capsules have been a focus our for last 15 years. This review describes solid state complexation studies unsubstituted phenolic pyrogall[4]arenes towards formation dimeric assemblies using ionic neutral species guest molecules templates. The multitude different...

Abstract Iodine (I 2 ) acts as a bifunctional halogen‐bond donor connecting two macrocyclic molecules of the bowl‐shaped acceptor, N ‐cyclohexyl ammonium resorcinarene chloride 1 , to form dimeric capsule [(1,4‐dioxane) 3 @ ]. The is constructed solely through halogen bonds and has single cavity ( V =511 Å large enough encapsulate three 1,4‐dioxane guest molecules.

The first examples of iodoethynyl resorcinarene cavitands as rigid 3D halogen bond (XB) donor molecules are presented. These concave macrocycles form strong, <italic>R</italic>_XB = 0.78–0.83, bonds with dioxane oxygen, pyridine nitrogen and a bromide anion in tetraproropyl ammonium resulting deep cavity cavitand structures.

<italic>N</italic>-Alkyl ammonium resorcinarene halides together with 1,4-diiodotetrafluorobenzene form a deep-cavity cavitand-like structure held by moderate halogen bonds. Each salt⋯(IC₆F₄I)₄ assembly acts as pocket for the next resulting in polymeric herringbone and 3-D egg-crate-like network.

N-Alkyl ammonium resorcinarene bromides and 1,4-diiodooctafluorobutane via multiple intermolecular halogen bonds (XB) form different exotic supramolecular architectures through subtle changes of the upper rim substituents. Dimeric dumbbell-like assembly with encapsulated guest molecules is generated N-benzyl The N-hexyl groups engender an XB-induced polymeric pseudocapsule dimeric capsule entrapped 1,4-dioxane molecules. N-propyl N-cyclohexyl generate deep cavity cavitands. cavitands possess...

A cationic pillararene-dye host–guest complex capable of heparin binding and sensing is presented.

Supramolecular self-assembly of biomolecules provides a powerful bottom-up strategy to build functional nanostructures and materials. Among the different biomacromolecules, protein cages offer various advantages including uniform size, versatility, multi-modularity, high stability. Additionally, cage crystals present confined microenvironments with well-defined dimensions. On other hand, molecular hosts, such as cyclophanes, possess defined cavity size selective recognition guest molecules....

Hydrogen/deuterium exchange (HDX) experiments can be used to examine the gas-phase structure of hydrogen-bonded dimeric resorcinarene and pyrogallarene capsules. Already qualitative comparison isotope rates different host–guest complexes with Cs+, tetramethyl ammonium (TMA+) tetraethyl (TEA+) as guest cations provides insight into H/D-exchange mechanisms it, capsules' ion structures. The smaller Cs+cations bind inside capsules an intact seam hydrogen bonds between two monomers. Larger such...

Abstract Resorcinarenes are cavity‐containing compounds when in the crown conformation, from calixarene family of concave compounds. These easy to synthesize macrocycles can be decorated at upper rim through eight hydroxyl groups and/or 2‐position aromatic ring. They good synthons supramolecular chemistry leading appealing assemblies such as open‐inclusion complexes, capsules and tubes multiple weak interactions with various guests. Halogen bonding (XB) is a highly directional non‐covalent...

Abstract N ‐Alkyl ammonium resorcinarene chlorides, stabilized by an intricate array of hydrogen bonds leading to a cavitand‐like structure, bind amides. The molecular recognition occurs through intermolecular between the carbonyl oxygen and amide guests cation–anion circular hydrogen‐bonded seam hosts, as well CH ⋅⋅⋅ π interactions. ‐alkyl chlorides cooperatively series di‐acetamides varying spacer lengths ranging from three seven carbons. Titration data fit either 1:1 or 2:1 binding...

Abstract Two [N⋅⋅⋅I + ⋅⋅⋅N] halogen‐bonded dimeric capsules using tetrakis(3‐pyridyl)ethylene cavitands with different lower rim alkyl chains are synthesized and analyzed in solution the gas phase. These first examples of symmetrical making use iodonium ion (I ) as main connecting module characterized by 1 H NMR spectroscopy, diffusion ordered spectroscopy (DOSY), electrospray ionization mass spectrometry (ESI‐MS), mobility‐mass (TW‐IMS) experiments. The synthesis effective dimerization...

"Survival of the fittest": Nur diejenigen hexameren Pyrogallaren- und Resorcinarenkapseln, die ein Gastkation der richtigen Größe, Gestalt Symmetrie enthalten (siehe Bild), überleben Elektrospray-Ionisation, ihre massenspektrometrische Detektion ermöglicht. Tandem-MS-Experimente mit massenselektierten Ionen belegen, dass Hexamere Kapselstruktur auch in Gasphase beibehalten.

The one-pot Mannich condensation of resorcinarenes with piperazine and an excess formaldehyde under high dilution conditions results in a helical cage, namely, covalently linked dimer two connected via four bridges yields ranging from 20 to 40%. compounds were analyzed by NMR spectroscopy, ESI mass spectrometry, single crystal X-ray diffraction. cages can encapsulate small guest molecules adapting the cavity volume changing pitch according size.