Subkomponenten‐Selbstorganisation und Transmetallierung zweikerniger Helikate

Abstract

Nur als Helikate erhältlich: Zweikernige Zink‐ und Nickelkomplexe mit bisher präparativ nicht zugänglichen N,S‐N,S‐Liganden wurden in Subkomponenten‐Selbstorganisationsreaktionen ausgehend von Komplexen mit zwei o‐Thiolatobenzaldehyd‐Liganden und 4,4′‐Diaminodiphenylmethan erhalten. Beide Komplexe bilden mit Pd(OAc)2 unter Transmetallierung den entsprechenden zweikernigen Palladiumkomplex (siehe Schema).

Solvent‐Dependent Host–Guest Chemistry of an Fe8L12 Cubic Capsule

“…In the antiparallel arrangement required to form an M 4 L 6 tetrahedron (Scheme 1 a), such a ligand would need to distort substantially in order to provide an octahedral coordination environment at the Fe II vertices, whereas an M 8 L 12 cube would be comparatively strain-free. Such a ligand could be prepared through the subcomponent self-assembly [14] of 3,[3][4]Scheme 2) and primary amines around Fe II ions, as was shown to work well for the Scheme 1. The differing orientations of the coordinate vectors [15] (arrows on the Fe II centers) of isomeric bis(pyridylimine) ligands bring about different self-assembled architectures.…”

“…The modularity of the subcomponent self-assembly approach [14] allows for differently substituted aniline residues to be incorporated into the cubic framework of 1. These anilines substituents offer a straightforward means to alter the physicochemical properties of the resulting assemblies.…”

Transformations within a Network of Cadmium Architectures

“…They include light, [4] pH value, [5] chemical templates, [6] temperature, [7] solvent, [8] and a change in concentration. [9] The use of subcomponent self-assembly [10] to construct complex metal-organic architectures [11] provides pathways for these structures to dynamically reassemble by taking advantage of enthalpic or entropic driving forces. [2,12] Herein, we examine how a system of diverse self-assembled cadmium(II) complexes responds to a variety of chemical signals to produce an array of multinuclear architectures.The system under study contains 4,4'-diformyl-3,3'-bipyridine (A), a variety of different amines, and cadmium triflate in acetonitrile solution.…”

Using Complementary Ligand Denticity to Direct Metallosupramolecular Structure about Metal Ions with Square‐Planar Geometry

“…In other cases, the ligand dimensions themselves favour the formation of complexes with a single arrangement around the metal ion. For example, Hahn and coworkers combined a bis ‐(2‐thiolatobenzaldehyde) Ni II complex with 4,4’‐diaminodiphenylmethane in a 2 : 2 ratio to give a neutral [Ni 2 L2 2 ] complex with 2‐imine‐benzenethialto chelators (Figure ) through imine condensation . The ligand ensures that, in the smallest possible [2+2] structure, only the head‐to‐head arrangement around the metal ions is possible (trace amounts of the larger [3+3] assembly were also present in equilibrium).…”

“… Formation of a [Ni 2 L2 2 ] complex from imine condensation where L2 is a bis ‐(2‐imine‐benzenethialato) ligand, followed by transmetallation to give the Pd II analogue. Depictions are of crystal structures reported by Hahn and coworkers . Colors: carbon gray or green, nickel light green, nitrogen blue, palladium dark blue, sulfur yellow.…”