0000000000282170
AUTHOR
Chulsoon Moon
Self-assembled dendrimers with uniform structure
Calix[4]arenes substituted at their wide rim by four aryl urea residues (1) form hydrogen-bonded dimers in apolar solvents. Replacement of one urea residue by an acetamido moiety leads to calix[4]arene derivatives (5) which form hydrogen-bonded tetramers under the same conditions. Both self-assembly processes occur independently. Therefore, molecules have been prepared in which a tetra-urea calix[4]arene and a tri-urea mono acetamide derivative are covalently connected between their narrow rims by a long, mainly aliphatic chain [-O-(CH(2))(n)-C(O)-NH-(CH(2))(m)-O-] (7). In the presence of an equimolar amount of tetra-tosyl urea calix[4]arene () they form dendritic assemblies since the well …
Electrochemical response of ferrocenium filled calix[4]arene capsules in solution and immobilized on gold
Abstract Hydrogen-bonded dimers of tetra-urea calix[4]arenes are able to include ferrocenium ions as a guest. Heterodimeric capsules are exclusively formed in 1:1 mixtures of tetra-arylurea calix[4]arene 1 with tetra-tosylurea calix[4]arene 2. Sulfide groups attached via spacers on the urea rim of 1 allow their binding to metal surfaces rendering simultaneously their dissociation more difficult. Thus, the electrochemical response of encapsulated ferrocenium could be studied in a self-assembled monolayer (SAM) in addition to the solution electrochemistry with cyclic voltammetry. The stability of the electrochemically active monolayers was tested after a heat treatment (225 °C for 30 min in N…
Solid-state NMR and computational studies of tetratolyl urea calix[4]arene inclusion compounds.
Solid-state guest dynamics of tetratolyl tetraurea calix[4]arene tetrapentylether dimeric capsules filled with different types of aromatic guests such as benzene-d6, fluorobenzene-d5 and 1,4-difluorobenzene were studied. Upon inclusion, all guest moieties revealed complexation-induced shifts varying from 2.8 ppm to 5.1 ppm. All guest molecules were shown to undergo distinct motions, ranging from mere C6-rotations of benzene-d6 to (ill-defined) 180 degrees phenyl flips of fluorobenzene-d5. In all cases, dynamic heterogeneities were identified based on 2H lineshape deconvolution. In addition, by combination of both a computed nucleus independent chemical shift (NICS) map and explicit 19F and …
Self-assembly of programmed building blocks into structurally uniform dendrimers.
Selective and independent dimerization of tri- and tetraurea derivatives was used to build up dendritic assemblies which are uniform in size and structure. Dendrimers with the total molecular masses of about 25 000 g/mol were obtained. The existence of uniform assemblies was proved by 1H and 1H DOSY NMR experiments and also by dynamic light scattering.