Monohydroxy alcohols show a structural relaxation and at longer time scales a Debye-type dielectric peak. From spin-lattice relaxation experiments using different nuclear probes an intermediate, slower-than-structural dynamics is identified for n-butanol. Based on these findings and on diffusion measurements, a model of self-restructuring, transient chains is proposed. The model is demonstrated to explain consistently the so far puzzling observations made for this class of hydrogen-bonded glass forming liquids.

Fullerenes and their derivatives are of tremendous technological relevance. Synthetic access and application are still hampered by tedious purification protocols, peculiar solubility, and limited control over regioselective derivatization. We present a modular self-assembly system based on a new low-molecular-weight binding motif, appended by two palladium(II)-coordinating units of different steric demands, to either form a [Pd2L14]4+ cage or an unprecedented [Pd2L23(MeCN)2]4+ bowl (with L1 = pyridyl, L2 = quinolinyl donors). The former was used as a selective induced-fit receptor for C60. The latter, owing to its more open structure, also allows binding of C70 and fullerene derivatives. By exposing only a fraction of the bound guests’ surface, the bowl acts as fullerene protecting group to control functionalization, as demonstrated by exclusive monoaddition of anthracene. In a hierarchical manner, sterically low-demanding dicarboxylates were found to bridge pairs of bowls into pill-shaped dimers, able to host two fullerenes. The hosts allow transferring bound fullerenes into a variety of organic solvents, extending the scope of possible derivatization and processing methodologies.

Control over the integrative self‐sorting of metallo‐supramolecular assemblies opens up possibilities for introducing increased complexity and function into a single self‐assembled architecture. Herein, the relationship between the geometry of three ligand components and morphology of three self‐sorted heteroleptic [Pd2 L 2 L′2]4+ cages is examined. Pd‐mediated assembly of two bis‐monodentate pyridyl ligands with native bite angles of 75° and 120° affords a cis‐[Pd2 L 2 L′2]4+ cage while the same reaction with two ligands with bite angles of 75° and 60° gives an unprecedented, self‐penetrating structural motif; a trans‐[Pd2(anti‐L)2 L′2]4+ heteroleptic cage with a “doubly bridged figure eight” topology. Each heteroleptic assembly can be formed by cage‐to‐cage conversion of the homoleptic precursors and morphological control of [Pd2 L 2 L′2] cages is achieved by selective ligand displacement transformations in a system of three ligands and at least six possible cage products.

The segmental and normal mode dynamics of poly(propylene glycol) (PPG) were studied using dielectric spectroscopy for a wide range of molecular weights. For intermediate chain lengths the normal mode spectra, unmasked by electrical purging procedures, were described quantitatively using the Rouse model. Based on the ratio of the dispersion strengths of the normal and of the segmental mode, the characteristic ratio C ¥ was determined. The spectral width of the segmental mode evolves smoothly with the number of repeat units N and, except for dipropylene glycol, so does the mean time scale. The exceptional behavior was confirmed by 13 C NMR relaxation experiments. For small N the segmental and the normal modes tend to merge near the glass transformation range. Exploiting the polymer chains as "molecular rulers", the growth of the characteristic length scale associated with the vitrification process is estimated for PPG. In the glassy state two dipolarly active relaxation processes were resolved. The slower one is characterized by an activation energy typical for hydrated systems, and its dispersion strength can be modified by appropriate heat treatment.

Dielectric loss spectra covering 13 decades in frequency were collected for 2-ethyl-1-hexanol, a monohydroxy alcohol that exhibits a prominent Debye-like relaxation, typical for several classes of hydrogen-bonded liquids. The thermal variation of the dielectric absorption amplitude agrees well with that of the hydrogen-bond equilibrium population, experimentally mapped out using near infrared (NIR) and nuclear magnetic resonance (NMR) measurements. Despite this agreement, temperature-jump NIR spectroscopy reveals that the hydrogen-bond switching rate does not define the frequency position of the prominent absorption peak. This contrasts with widespread notions and models based thereon, but is consistent with a recent approach.