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The multifunctional rigid-rod Beta-barrel pores offers a good platform to study chemical processes that take place within their confined, oriented, inert and functionalized internal nanospace. The first molecular mechanics modeling (MacroModel, MMFF94) of multifunctional rigid-rod Beta-barrel pore hosts 1 with internal 1,3,6-pyrenetrisulfonate guests is reported.

Supra-molecular architectures containing lanthanide ions because of their intrinsic magnetic, spectroscopic, and optical properties are focused. It is shown that absorption spectra, combined with electrochemical data, demonstrate the dual effect associated with attachment of the sulfonamide group.

The first oriented multicolored antiparallel redox gradients (OMARG-SHJs) with two-component redox gradients are described in both the electron- and hole-transporting pathways. The presence of both gradients is essential for achieving photoinduced charge separation over very long distances.

The synthesis, characterization, and zipper assembly of yellow p-oligophenyl naphthalenediimide (POP-NDI) donor-acceptor hybrids are described. The results suggested that characteristics such as significant critical thickness, strong photocurrents, large fill factors, and smooth surfaces are important for optoelectronic performance and support of the existence of highly ordered architectures.

The studies related to design, synthesis, oxidation potentials and quadrupole moments of a complete collection of dialkoxynaphthalenes (DAN) and DAN amplifiers is reported. The results demonstrate that synthetic pores that operate by ion-pair-assisted [pi]-clamping are capable of regioisomer recognition responding to structural differences as subtle as the one between 2,6- and 2,7-DAN isomers.

A report on the design, synthesis, and evaluation of multifunctional pores with electron-deficient naphthalenediimide (NDI) [pi]-clamps at their inner surface for molecular recognition by aromatic electron donor-acceptor interactions is presented. The [pi]-clamping by aromatic electron donor-acceptor interactions is introduced as an attractive concept to complement molecular recognition within synthetic multifunctional pores with interactions.

The plum-colored charge-transfer complexes formed by dialkoxynaphthalene (DAN) donors and naphthalenediimide (NDI) acceptors are introduced to create synthetic ion channels with a novel rigid-rod pi-stack architecture that open in response to guest binding. The results obtained confirmed the potential of the new rigid-rod pi-stack architecture to expand the practical usefulness of synthetic multifunctional ion channels and pores toward electron-transfer processes.

The synthetic multifunctional pore that opens rather than close in response to chemical stimulation is reported. The rational design of synthetic multifunctional pores can be of practical use for the continuous fluorometric detection of chemical processes.

The design, synthesis and evaluation of [pi]-acidic, shape-persistent oligo-(p-phenylene)-N,N-naphthalenediimide (O-NDI) rods are reported that can transport anions across lipid bilayer membranes with rare halide VI selectivity and a substantial anomalous mole fraction effect (AMFE). The rare halide VI sequence of neutral O-NDI rods, together with reduced selectivity and halide sequence but increased activity with one cationic rod terminus, are in agreement with operational dynamic anion-[pi] interactions.

Of central importance in chemistry and biology, enolate chemistry is an attractive topic to elaborate on possible contributions of anion-π interactions to catalysis. To demonstrate the existence of such contributions, experimental evidence for the stabilization of not only anions but also anionic intermediates and transition states on π-acidic aromatic surfaces is decisive. To tackle this challenge for enolate chemistry with maximal precision and minimal uncertainty, malonate dilactones are covalently positioned on the π-acidic surface of naphthalenediimides (NDIs). Their presence is directly visible in the upfield shifts of the α-protons in the 1H NMR spectra. The reactivity of these protons on π-acidic surfaces is measured by hydrogen-deuterium (H-D) exchange for 11 different examples, excluding controls. The velocity of H-D exchange increases with π acidity (NDI core substituents: SO2R>SOR>H>OR>OR/NR2>SR>NR2). The H-D exchange kinetics vary with the structure of the enolate (malonates>methylmalonates, dilactones>dithiolactones). Moreover, they depend on the distance to the π surface (bridge length: 11-13 atoms). Most importantly, H-D exchange depends strongly on the chirality of the π surface (chiral sulfoxides as core substituents; the crystal structure of the enantiopure ( R, R, P)-macrocycle is reported). For maximal π acidity, transition-state stabilizations up to −18.8 kJ mol−1 are obtained for H-D exchange. The Brønsted acidity of the enols increases strongly with π acidity of the aromatic surface, the lowest measured p Ka=10.9 calculates to a Δp Ka=−5.5. Corresponding to the deprotonation of arginine residues in neutral water, considered as 'impossible' in biology, the found enolate-π interactions are very important. The strong dependence of enolate stabilization on the unprecedented seven-component π-acidity gradient over almost 1 eV demonstrates quantitatively that such important anion-π activities can be expected only from strong enough π acids. [ABSTRACT FROM AUTHOR]

A Fourier transform ion cyclotron resonance spectroscopic study based on dissociative proton attachment of bridgehead bromides, chlorides and alcohols was conducted to determine the gas-phase stability of bridgehead carbocations. Results confirm the original hypothesis that bridgehead derivatives solvolyse by a common mechanism and that the stability of the intermediate carbenium ions is reflected in the transition state of the reaction.

The back cover of the journal "Angewandte Chemie" is presented.

Lipophilic methyl‐substituted cyanobiphenyls can be considered as molecular salmon that jump out of the condensed phase, but are limited by an increase in size of their rigid core. The concept of cohesive free‐energy densities applied to melting processes correlates the molecular volumes of the constituents with the macroscopic enthalpic and entropic changes that accompany the phase transitions of the bulk materials. For more details see the Full Paper by E. Terazzi, C. Piguet et al. on page 8447 ff. [ABSTRACT FROM AUTHOR]