Bending Nanofibers into Nanospirals: Coordination Chemistry as a Tool for Shaping Hydrophobic Assemblies

In the current work, we demonstrate how coordination chemistry can be employed to direct self‐assembly based on strong hydrophobic interactions. To investigate the influence of coordination sphere geometry on aqueous self‐assembly, we synthesized complexes of the amphiphilic perylene diimide terpyridine ligand with the first‐row transition‐metal centers (zinc, cobalt, and nickel). In aqueous medium, aggregation of these complexes is induced by hydrophobic interactions between the ligands. However, the final shapes of the resulting assemblies depend on the preferred geometry of the coordination spheres typical for the particular metal center. The self‐assembly process was characterized by UV/Vis spectroscopy, zeta potential measurements, and cryogenic transmission electron microscopy (cryo‐TEM). Coordination of zinc(II) and cobalt(II) leads to the formation of unique nanospiral assemblies, whereas complexation of nickel(II) leads to the formation of straight nanofibers. Notably, coordination bonds are utilized not as connectors between elementary building blocks, but as directing interactions, enabling control over supramolecular geometry.     

Kelley-Morse+Types of well order is not a conservative extension of Kelley Morse

Summary Assuming the consistency ofZF + There is an inaccessible number of inaccessibles, we prove that Kelley Morse theory plus types is not a conservative extension of Kelley-Morse theory.This paper was partially supported by: Dirección de Investigación de la Pontificia Universidad Católica de Chile (DIUC); Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT)     

Filling factor in a pulsed electron paramagnetic resonance experiment

A definition and mathematical treatment to calculate the filling factor in a pulsed electron paramagnetic resonance (EPR) experiment are presented. The differences between filling factors in traditional, continuous wave (CW)-EPR experiments (eta), and in pulsed-EPR experiments (eta(p)), are discussed. We present some examples to demonstrate how eta(p) depends upon the particular pulse sequence and sample characteristics.     

Designed Enclosure Enables Guest Binding Within the 4200 Å3 Cavity of a Self‐Assembled Cube

Metal–organic self‐assembly has proven to be of great use in constructing structures of increasing size and intricacy, but the largest assemblies lack the functions associated with the ability to bind guests. Here we demonstrate the self‐assembly of two simple organic molecules with Cd^II and Pt^II into a giant heterometallic supramolecular cube which is capable of binding a variety of mono‐ and dianionic guests within an enclosed cavity greater than 4200 ų. Its structure was established by X‐ray crystallography and cryogenic transmission electron microscopy. This cube is the largest discrete abiological assembly that has been observed to bind guests in solution; cavity enclosure and coulombic effects appear to be crucial drivers of host–guest chemistry at this scale. The degree of cavity occupancy, however, appears less important: the largest guest studied, bound the most weakly, occupying only 11 % of the host cavity.