Frontispiece: An Octanuclear Metallosupramolecular Cage Designed To Exhibit Spin-Crossover Behavior
Ein achtkerniger metallosupramolekularer Würfel mit Spin-Crossover-Eigenschaften
From attraction to repulsion : anion–π interactions between bromide and fluorinated phenyl groups
Anion–π interactions in crystals of fluorobenzyl ammonium salts depend on the degree of fluorination at the aromatics.
Enantiomerenreine [M6L12]- oder [M12L24]-Polyeder aus flexiblen Bis(pyridin)-Liganden
Enantiomerically pure [M(6)L(12)] or [M(12)L(24)] polyhedra from flexible bis(pyridine) ligands.
Coordination-driven self-assembly is one of the most powerful strategies to prepare nanometer-sized discrete (supra)molecular assemblies. Herein, we report on the use of two constitutionally isomeric BINOL-based bis(pyridine) ligands for this purpose. Upon coordination to Pd(II) ions these self-assemble into enantiomerically pure endo- and exo-functionalized hexa- and dodecanuclear metallosupramolecular spheres with a chiral skeleton depending on the substitution pattern of the BINOL core. These aggregates were characterized by NMR, MS, DLS, TEM, and EELS as well as ECD. Furthermore, experimental ECD data could be compared to those obtained from theoretical simulations using a simplified Ta…
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