Size matters! The structure and dynamics of the tetratolyl Group 14 elements, which were probed by using high‐resolution inelastic neutron scattering spectra, show a remarkable dependence on the size of the central atom. The para‐methyl groups at the periphery of the molecules constitute the frontier intermolecular interactions of increasingly larger tetrahedra, which becomes critical at the molecular radius of the Si and Ge analogues (see picture).
Recycling of “green” solvents : Recycling of ionic liquids with high efficiency is of key importance on going from the laboratory‐scale to large‐scale industrial application of these solvents.
Spot the difference : The five‐coordinate iron(II) cyanoporphyrinates, which are spin‐crossover compounds, can be used to synthesize previously unknown six‐coordinate complexes. Bis(cyano) and (cyano)imidazole complexes are presented, and the five‐ and six‐coordinate (cyano)iron(II) derivatives are compared with analogous CO complexes.
Going separate ways : By using π‐allyl–palladium chemistry (path A) and PdII‐catalyzed Claisen chemistry (path B), a highly selective stereodivergent synthesis of separable amide rotamers was achieved (see scheme).
On an atomic scale and with high sensitivity, solid‐state NMR spectroscopy can provide information about the electronic spin density and coupling mechanisms in paramagnetic compounds. The picture shows how the hyperfine splitting collapses through relaxation. Insights into which compounds are suitable and which approximations have to be made are given.
Leading light : A series of zinc(II) bis‐terpyridine complexes (see picture) is investigated by means of DFT calculations combined with Bader's quantum theory of atoms in molecules. Raman spectroscopy experiments and studies of the electro‐optical properties of the complexes in solution and the solid state are also performed to examine their potential as new emissive materials in light‐emitting devices.
A growing attachment : Porous coordination polymer (PCP) nanorods are synthesized by modulation of the coordination equilibria between framework components, which regulates the rate of framework extension and crystal growth. Investigation of the crystal growth mechanism by TEM indicates that face‐selective modulation on the surfaces of PCP crystals enhances the anisotropic crystal growth of nanorods by an oriented attachment mechanism.
Triangular luminescent box : Self‐assembly of a new multidentate receptor with europium cations results in the formation of trinuclear discrete complexes. X‐ray crystallography shows that nine‐coordinate cations are linked by ligands to provide a triangular complex in the solid state and in solution. Despite the coordinated solvent molecules, this topologically unusual complex exhibits remarkable luminescent properties.
Secondary, but second to none : The use of secondary alkyl halides in transition‐metal‐catalyzed cross‐coupling reactions (see scheme) has advanced significantly over the last five years. Selected examples of these transformations are examined, including mechanistic and stereochemical aspects.
Building a better library : The synthesis of a library of natural‐product‐like small molecules with unprecedented scaffold diversity has been reported (see scheme; Ns=nosylate). The library represents a significant advancement in the capability of synthetic chemists to generate structurally diverse and complex small molecules in a rapid manner.
