The combination of pyridyl ligands and square-planar Pd(ii) or Pt(ii) cations has proven to be a very reliable recipe for the realization of supramolecular self-assemblies. This tutorial review deals with the design, synthesis and host-guest chemistry of discrete coordination cages built according to this strategy. The focus is set on structures obeying the formula [PdnL2n] (n = 2-4). The most discussed ligands are bent, bis-monodentate bridges having their two donor sites pointing in the same direction. The structures of the resulting cages range from simple globules over intertwined knots to interpenetrated dimers featuring three small pockets instead of one large cavity. The cages have large openings that allow small guest molecules to enter and leave the cavities. Most structures are cationic and thus favour the uptake of anionic guests. Some examples of host-guest complexes are discussed with emphasis on coencapsulation and allosteric binding phenomena. Aside from cages in which the ligands have only a structural role, some examples of functional ligands based on photo- and redox-active backbones are presented.

Recent developments show encouraging results for the use of DNA as a construction material for nanometer-sized objects. Today, however, DNA-based molecular nanoarchitectures are constructed with mainly unmodified or at best end-modified oligonucleotides, thus shifting the development of functionalized DNA structures into the limelight. One of most recent developments in this direction is the substitution of the canonical Watson-Crick base pairs by metal complexes. In this way "metal-base pairs" are created, which could potentially impart magnetic or conductive properties to DNA-based nanostructures. This review summarizes research which started almost 45 years ago with the investigation of how metal ions interact with unmodified DNA and which recently culminated in the development of artificial ligand-like nucleobases so far able to coordinate up to ten metal ions inside a single DNA duplex in a programmable fashion.

No abstract

Chemists of all fields currently publish about 50 000 crystal structures per year, the vast majority of which are X‐ray structures. We determined two molecular structures by employing electron rather than X‐ray diffraction. For this purpose, an EIGER hybrid pixel detector was fitted to a transmission electron microscope, yielding an electron diffractometer. The structure of a new methylene blue derivative was determined at 0.9 Å resolution from a crystal smaller than 1×2 μm 2 . Several thousand active pharmaceutical ingredients (APIs) are only available as submicrocrystalline powders. To illustrate the potential of electron crystallography for the pharmaceutical industry, we also determined the structure of an API from its pill. We demonstrate that electron crystallography complements X‐ray crystallography and is the technique of choice for all unsolved cases in which submicrometer‐sized crystals were the limiting factor.