The well-known unsubstituted "Hamilton receptor" was monofunctionalized with an amino group and attached at the periphery of poly(propyleneamine) dendrimers through the use of an activated ester. Four generations of Hamilton-receptor-functionalized dendrimers (HR-dendrimers) were synthesized and characterized by (1)H and (13)C NMR spectroscopy and MALDI-TOF mass spectrometry. The photophysical properties of the HR-dendrimers were investigated by UV/Vis as well as with steady-state and time-resolved fluorescence spectroscopy. The dendrimers were used as multivalent hosts for the barbiturate guests Barbital (7) and [Re(Br)(CO)(3)(barbi-bpy)] (8; barbi-bpy=5-[4-(4'-methyl)-2,2'-bipyridyl]methyl-2,4,6-(1 H,3 H,5 H)-pyrimidinetrione). The stable adducts formed between the dendritic architectures (the hosts) and the barbiturate guests 7 and 8 were investigated by (1)H NMR spectroscopy and photophysical methods. The binding constants of the barbiturate guests for binding to reference compound 2 (with a single receptor unit) in chloroform were found to be 1.4 x 10(3) M(-1) and 1.5 x 10(5) M(-1) for 7 and 8, respectively. Binding of 7 to the dendrimers enhances the weak emission of the Hamilton receptor. This increase in emission is also generation dependent; it was found to be most pronounced in the case of 2 and the least in the case of the fourth-generation dendrimer 6. The unexpected increase in the quantum yield of emission from the HR-dendrimers with increasing generation could be caused by the rather rigid conformation of the Hamilton receptors in later-generation compounds, which is a result of intramolecular aggregation and steric hindrance at the periphery of the dendrimer. The photoinduced energy transfer from the excited state of the HR-dendrimers to the lower-lying excited state of the guest 8 was used to probe the formation of host-guest complexes. The rate of energy transfer was calculated to be 3.6 x 10(10) s(-1). Energy transfer in 2 subset 8 only occurred in the presence of a strong base, which shows that the basic amine core in the HR-dendrimers is crucial for this photoinduced process. The binding of 8 to the dendrimers is completely reversible: 8 can be exchanged with a competitive guest such as 7 and the emission of the HR-dendrimer is restored.

A new pathway for the supramolecular synthesis of oligocatenanes is developed. It is based on a combination of most suitable macrocyclic structural units, obtained from tert-butyl-substituted isophthalic acid and terephthalic acid building blocks. These structural parts guarantee, on the one hand, the solubility of the catenanes and their intermediates, and, on the other hand, the preferred formation of larger ring sizes of the macrocycles to be intertwined. Acting as monotopic and ditopic concave templates, the tetra-and octalactam macrocycles were submitted to threading procedures to yield higher-order catenanes of the amide type. By repetition of the threading steps, it was possible to isolate multiply mechanically connected [n]catenanes up to n 4 composed of various macrocyclic units.

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Strategies towards the synthesis of well‐defined, mechanically interlocked, dendritic assemblies of rotaxanes are developed, one using a divergent, and the other a convergent approach. For the first time covalent bonds are not directly involved in the branching of dendrimers, only mechanical bonds act as unique branching elements.

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