Self-assembled phenylethynylene bis-urea macrocycles facilitate the selective photodimerization of coumarin.

There is much interest in designing molecular sized containers that influence and facilitate chemical reactions within their nanocavities. On top of the advantages of improved yield and selectivity, the studies of reactions in confinement also give important clues that extend our basic understanding of chemical processes. We report here, the synthesis and self-assembly of an expanded bis-urea macrocycle to give crystals with columnar channels.

Examination of the structural features that favor the columnar self-assembly of bis-urea macrocycles.

Second-generation self-assembling bis-urea macrocycles were designed that form columnar structures in the solid state. The new macrocycles were constructed from more flexible building blocks yielding greater solubility and a more efficient synthesis. In addition, heteroatoms in the form of ether oxygens were incorporated in the walls of the macrocycles to provide additional recognition sites for guest encapsulation.

A synthetic host-guest system achieves avidin-biotin affinity by overcoming enthalpy-entropy compensation.

The molecular host cucurbit[7]uril forms an extremely stable inclusion complex with the dicationic ferrocene derivative bis(trimethylammoniomethyl)ferrocene in aqueous solution. The equilibrium association constant for this host-guest pair is 3 x 10(15) M(-1) (K(d) = 3 x 10(-16) M), equivalent to that exhibited by the avidin-biotin pair. Although purely synthetic systems with larger association constants have been reported, the present one is unique because it does not rely on polyvalency.

New dendrimers containing a single cobaltocenium unit covalently attached to the apical position of Newkome dendrons: electrochemistry and guest binding interactions with cucurbit[7]uril.

Two new dendrimer series were prepared and characterized. These dendrimers contain a single bis(cyclopentadienyl)cobalt(III) (cobaltocenium, Cob+) unit covalently attached to the apical (focal) position of Newkome-type dendrons, ranging in size from first to third generation. The dendrimers in the first series (1ECob+-3ECob+) are hydrophobic and have 3, 9, and 27 tert-butyl esters on their peripheries, whereas the dendrimers in the second series (1Cob+-3Cob+) are hydrophilic with 3, 9, and 27 carboxylic acid groups on their surfaces, respectively.

Electrochemically switchable cucurbit[7]uril-based pseudorotaxanes.

[Structure: see text] The binding location of cucurbit[7]uril can be controlled via redox conversions in these novel, structurally simple pseudorotaxanes.

Binding interactions between the host cucurbit[7]uril and dendrimer guests containing a single ferrocenyl residue.

The stability of the inclusion complexes formed between the host cucurbit[7]uril and dendrimers containing a single ferrocene residue is strongly affected by the solution pH and the growth of the dendrimer, reaching its highest values on the second and third generation dendrimers, whereas no complex is formed with the first generation compound.

Complexation of ferrocene derivatives by the cucurbit[7]uril host: a comparative study of the cucurbituril and cyclodextrin host families.

The formation of inclusion complexes between cucurbit[7]uril (CB[7]) and ferrocene and its derivatives has been investigated. The X-ray crystal structure of the 1:1 inclusion complex between ferrocene and CB[7] revealed that the guest molecule resides in the host cavity with two different orientations. Inclusion of a set of five water-soluble ferrocene derivatives in CB[7] was investigated by 1H NMR spectroscopy and calorimetric and voltammetric techniques.

Electrochemical and guest binding properties of Frechet- and Newkome-type dendrimers with a single viologen unit located at their apical positions.

Several new series of dendrimers containing a single redox-active 4,4'-bipyridinium (viologen) residue were synthesized and characterized. In these dendrimers, the viologen group is covalently attached to the apical position of a Newkome- or Frechet-type dendron, ranging in size from first to third generation of growth. The half-wave potentials corresponding to the two consecutive one-electron reductions of the viologen residue are affected by the size of the dendritic component.

Sulfide-capped wire-like metallaynes as connectors for Au nanoparticle assemblies.

A new series of Ru2(DMBA)4(oligo(phenyleneethyne))2 compounds bearing sulfide termini was synthesized; structural characterization revealed both the rigid rod nature and extended pi-conjugation in these metallaynes; in the presence of these metallaynes, Au nanoparticles readily assembled into dimers and chains with well-defined inter-dimer distances.