Incarceration of (PdO)_n and Pd_n Clusters by Cage‐Templated Synthesis of Hollow Silica Nanoparticles

Abstract

Ein sphärischer Pd12L24‐Komplex dient als Templat bei der Synthese von hohlen Siliciumdioxidnanopartikeln, die Metallcluster mit definierter Atomzahl n in ihrem Inneren enthalten. Der eingeschlossene Pd12L24‐Komplex wird in der schützenden Siliciumdioxidhülle zunächst in einen (PdO)n‐Oxidcluster umgewandelt und anschließend zum Pdn‐Metallcluster reduziert.

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

“…The applications of metal–organic polyhedral container molecules1 include gas storage and separation,2 nanoparticle templation,3 catalysis,4 and the protection of sensitive guests 5. The promise of new functions and applications motivates much current interest in this class of compounds 6.…”

Enantiomerically Pure [M6L12] or [M12L24] Polyhedra from Flexible Bis(Pyridine) Ligands

“…[2] The use of tetravalent Pd II and Pt II acceptors and rigid ditopic bridging N-donor ligands, for instance, has been demonstrated to give rise to three dimensional [M n L 2n ] assemblies [3][4][5][6][7][8] with n ranging from two up to even twentyfour in a relatively reliable manner following the general assumption that the smallest assembly forms in which all the coordination sites on the metal centers and the ligands are occupied (the maximum occupancy rule) that does not experience too much steric strain. [9,10] What has not been established yet is the construction of a palladium-or platinum-containing metallosupramolecular assembly with six or more metal atoms and an inherently chiral ligand leading to a chiral spherical metallosupramolecular framework rather than a non-chiral sphere with chiral groups on the endo-or exo-side of the assembly. [6][7][8] However, this approach is not only interesting from a conceptual point of view but it is also very attractive for a number of applications because functionalized ligands can lead to endo-or exo-functionalized assemblies with interesting properties.…”

“…[6][7][8] However, this approach is not only interesting from a conceptual point of view but it is also very attractive for a number of applications because functionalized ligands can lead to endo-or exo-functionalized assemblies with interesting properties. [9,10] What has not been established yet is the construction of a palladium-or platinum-containing metallosupramolecular assembly with six or more metal atoms and an inherently chiral ligand leading to a chiral spherical metallosupramolecular framework rather than a non-chiral sphere with chiral groups on the endo-or exo-side of the assembly. [9d,h,j, 10a-c] Hence, we decided to prepare two constitutionally isomeric bis(pyridine) ligands 1 and 2 based on a chiral 2,2'-dihydroxy-1,1'-binaphthyl (BINOL) core, both in enantiomerically pure P-and M-forms and racemic forms, and study their selfassembly to metal-organic [M n L 2n ] polyhedra upon coordination to [Pd(CH 3 CN) 4 ](BF 4 ) 2 .…”

Enantiomerenreine [M6L12]‐ oder [M12L24]‐Polyeder aus flexiblen Bis(pyridin)‐Liganden

“…[6][7][8] Dabei ist dieser Ansatz aber nicht nur konzeptionell interessant, sondern auch wegen der vielfältigen Anwendungen sehr attraktiv, da man bei der Verwendung von funktionalisierten Liganden zu endo-oder exo-funktionalisierten Aggregaten mit interessanten Eigenschaften gelangen kann. [9,10] Was bislang noch nicht realisiert werden konnte, ist die Konstruktion eines metallosupramolekularen Aggregats mit sechs oder mehr Palladium-oder Platinatomen, das aus einem inhärent chiralen Liganden gebildet wird und folglich ein chirales sphärisches metallosupramolekulares Gerüst aufweist und nicht aus einer achiralen Sphäre mit exo-oder endoständigen chiralen Gruppen besteht. [9d,h,j, 10a-c] Die Synthese der chiralen Liganden geht von (M)-oder (P)-3,3'-oder -6,6'-diiod-2,2'-bis(methoxymethoxy)-1,1'-binaphthyl aus, die zuvor nach bekannten Verfahren hergestellt wurden.…”