Frontispiece: An Octanuclear Metallosupramolecular Cage Designed To Exhibit Spin-Crossover Behavior

Ein achtkerniger metallosupramolekularer Würfel mit Spin-Crossover-Eigenschaften

Chiral self-sorting behaviour of [2.2]paracyclophane-based bis(pyridine) ligands

Two constitutionally isomeric chiral bis(pyridine) ligands based on planar chiral 4,15-difunctionalized [2.2]paracyclophanes were synthesized, the respective enantiomers were separated via HPLC on a chiral stationary phase, and their self-assembly behaviour upon coordination to palladium(ii) ions was studied with regard to chiral self-sorting effects. As proven by NMR spectroscopy, mass spectrometry, CD spectroscopy, UV-Vis spectroscopy and X-ray crystallography both ligands form the expected dinuclear complexes upon coordination to cis-protected di- or tetravalent palladium(ii) ions, respectively, however, with distinct differences concerning their chiral self-sorting ability. peerReviewed

An Octanuclear Metallosupramolecular Cage Designed To Exhibit Spin-Crossover Behavior.

By employing the subcomponent self-assembly approach utilizing 5,10,15,20-tetrakis(4-aminophenyl)porphyrin or its zinc(II) complex, 1H-4-imidazolecarbaldehyde, and either zinc(II) or iron(II) salts, we were able to prepare O-symmetric cages having a confined volume of ca. 1300 Å3 . The use of iron(II) salts yielded coordination cages in the high-spin state at room temperature, manifesting spin-crossover in solution at low temperatures, whereas corresponding zinc(II) salts led to the corresponding diamagnetic analogues. The new cages were characterized by synchrotron X-ray crystallography, high-resolution mass spectrometry, and NMR, Mössbauer, IR, and UV/Vis spectroscopy. The cage structures…

CCDC 1451726: Experimental Crystal Structure Determination

Related Article: Niklas Struch, Christoph Bannwarth, Tanya K. Ronson, Yvonne Lorenz, Bernd Mienert, Norbert Wagner, Marianne Engeser, Eckhard Bill, Rakesh Puttreddy, Kari Rissanen, Johannes Beck, Stefan Grimme, Jonathan R. Nitschke, Arne Lützen|2017|Angew.Chem.,Int.Ed.|56|4930|doi:10.1002/anie.201700832