Phenanthroline‐ and Terpyridine‐Substituted Tetralactam Macrocycles: A Facile Route to Rigid Di‐ and Trivalent Receptors and Interlocked Molecules

  title={Phenanthroline‐ and Terpyridine‐Substituted Tetralactam Macrocycles: A Facile Route to Rigid Di‐ and Trivalent Receptors and Interlocked Molecules},
  author={Egor V. Dzyuba and Bilge Baytekin and Dominik Sattler and Christoph A. Schalley},
  journal={European Journal of Organic Chemistry},
Bromo-substituted Hunter/Vogtle-type tetralactam macrocycles (TLMs) represent key intermediates for the attachment of terpyridyl and phenanthroline metal binding sites through cross-coupling reactions. From these monovalent precursors, metal complexes can easily be obtained that present the macrocycles in a multivalent fashion. Depending on the nature of the metal ion, the properties of the complexes can be tuned with respect to valency (e.g., phen-TLM + CuI: divalent, phen-TLM + FeII… Expand
4 Citations
Efficient Self-Assembly of Di-, Tri-, Tetra-, and Hexavalent Hosts with Predefined Geometries for the Investigation of Multivalency.
Preliminary isothermal calorimetry (ITC) titrations provided promising results, which indicated the host complexes under study to be suitable for the future investigation of multivalent and cooperative binding. Expand
Active-template synthesis of “click” [2]rotaxane ligands: self-assembly of mechanically interlocked metallo-supramolecular dimers, macrocycles and oligomers
Due to potential applications in the biological and material sciences there is considerable interest in the development of mechanically interlocked ligands (MILs). The mild functional-group tolerantExpand
A switchable [2]rotaxane with two active alkenyl groups
A novel functional [2]rotaxane containing two alkenyl bonds was designed, synthesized and characterized by 1H, 13C NMR spectroscopy and HRESI mass spectrometry, providing a powerful platform for preparing stimuli-responsive polymers. Expand
Transformations within a network of cadmium architectures.
CdII transformer: By using a linear dialdehyde, CdII ions, and different amines, different architectures were constructed, including an M2L3 4+ triple helicate, an M 3L3 6+ triangle, an M4L8+Expand


Tetra- and octalactam macrocycles and catenanes with exocyclic metal coordination sites: versatile building blocks for supramolecular chemistry.
The synthesis of a new tetralactam Macrocycle and the simultaneous formation of catenanes and larger octalactam macrocycles is reported, allowing an unequivocal identification of the catenane and octalacts structures, despite the fact that both have the same elemental composition and bear identical structural subunits. Expand
The magic effect of endocyclic but non-sterically hindering biisoquinoline chelates: From fast-moving molecular shuttles to (3)rotaxanes
Abstract The use of 8,8′-diaryl-substituted 3,3′-biisoquinolines allows the construction of new multi-component assemblies that are inaccessible with the 2,9-diaryl-substituted 1,10-phenanthrolineExpand
A Synthetic Approach Towards Interlocked π-Conjugated Macrocycles†
A method for the synthesis of interlocked π-conjugated macrocycles is described. Starting from 2,9-bis(oligothienyl)[1,10]phenanthrolines, (trimethylsilyl)acetylene groups were introduced at theExpand
Diels-Alder active-template synthesis of rotaxanes and metal-ion-switchable molecular shuttles.
Unusually for an active-template synthesis, the metal binding site "lives on" in these rotaxanes, and was exploited in the synthesis of a molecular shuttle containing two different ligating sites in which the position of the macrocycle could be switched by complexation with metal ions with different preferred coordination geometries. Expand
Effects of subtle differences in ligand constitution and conformation in metallo-supramolecular self-assembled polygons.
3,3'-Bis(pyridin-[n]-ylethynyl)biphenyl and the corresponding 2,2'-bipyridines assemble with (dppp)Pt(II) triflate into metallo-supramolecular polygons, which leads to different equilibrium products depending on the position of the terminal pyridine N atoms. Expand
[2]Pseudorotaxane and [2]rotaxane molecular shuttles: self-assembly through second-sphere coordination of thiocyanate ligands.
A Pd(Py)(2)(SCN)(2) complex is shown to form a [2]pseudorotaxane complex with a macrocyclic tetralactam, which binds in the solid state through an unexpected complexation geometry. The intermolecularExpand
Helicate, macrocycle, or catenate: Dynamic topological control over subcomponent self-assembly.
An additional closed topology became accessible through the use of a diamine that incorporates two rigid phenylene spacer groups between a flexible chain and the imine-forming nitrogen atoms, making the formation of a single macrocycle energetically disfavoured. Expand
Conformational flexibility of tetralactam macrocycles and their intermolecular hydrogen-bonding patterns in the solid state.
Analysis of the conformational properties of tetralactam macrocycles shows a remarkable degree of conformational flexibility, which substantially contribute to the understanding of the adaptability of macrocyclic scaffolds, which is crucial for guest binding or templated syntheses with TLMs. Expand
Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds
B. Other Catalyti; Process by Transition-Metal Complexes IV. Cross-Coupling Reaction A. Coupling of 1 -Alkenylboron Derivatives: Synthesis of Conjugated Dienes 6. Coupling of Arylboron Derivatives:Expand
A modular "toolbox" approach to flexible branched multimacrocyclic hosts as precursors for multiply interlocked architectures.
A modular "toolbox" strategy is presented that allows several tetralactam macrocycles to be covalently connected with each other or with a central spacer, and the macrocycle to be substituted with or connected to different chromophores, and metal-coordination sites to be attached to the macrocycles. Expand