No abstract

No abstract

A self-assembled coordination cage usually possesses one well-defined three-dimensional (3D) cavity whereas infinite number of 3D-cavities are crafted in a designer metal-organic framework. Construction of a discrete coordination cage possessing multiple number of 3Dcavities is a challenging task. Here we report the peripheral decoration of a trinuclear [Pd 3 L 6 ] core with one, two and three units of a [Pd 2 L 4 ] entity for the preparation of multi-3D-cavity conjoined-cages of [Pd 4 (L a) 2 (L b) 4 ], [Pd 5 (L b) 4 (L c) 2 ] and [Pd 6 (L c) 6 ] formulations, respectively. Formation of the tetranuclear and pentanuclear complexes is attributed to the favorable integrative self-sorting of the participating components. Cage-fusion reactions and ligand-displacement-induced cage-to-cage transformation reactions are carried out using appropriately chosen ligand components and cages prepared in this work. The smaller [Pd 2 L 4 ] cavity selectively binds one unit of NO 3 − , F − , Cl − or Br − while the larger [Pd 3 L 6 ] cavity accommodates up to four DMSO molecules. Designing aspects of our conjoined-cages possess enough potential to inspire construction of exotic molecular architectures.

Mimicking biological structures such as fruits and seeds using molecules and molecular assemblies is a great synthetic challenge. Here we report peanut-shaped nanostructures comprising two fullerene molecules fully surrounded by a dumbbell-like polyaromatic shell. The shell derives from a molecular double capsule composed of four W-shaped polyaromatic ligands and three metal ions. Mixing the double capsule with various fullerenes (that is, C60, C70 and Sc3N@C80) gives rise to the artificial peanuts with lengths of ∼3 nm in quantitative yields through the release of the single metal ion. The rational use of both metal–ligand coordination bonds and aromatic–aromatic π-stacking interactions as orthogonal chemical glue is essential for the facile preparation of the multicomponent, biomimetic nanoarchitectures.

Metal-driven self-assembly is one of the most effective approaches to lucidlydesign alarge range of discrete 2D and 3D coordinationa rchitectures/complexes. Palladium(II)-based self-assembled coordination architectures are usually preparedb yu sing suitable metal components, in either ap artially protected form (PdL')o rt ypical form (Pd; charges are not shown), and designed ligand components. The self-assembled moleculesp repared by using am etal component and only one type of bi-or polydentate ligand (L) can be classified in the homoleptic series of complexes. On the other hand, the less explored heteroleptic series of complexes are obtained by using am etal component and at least two different types of non-chelating bi-or polydentate ligands (such as L a andL b ). Methods that allow the controlled generation of single, discrete heteroleptic complexes are less understood.As urvey of palladium(II)-based self-as-sembled coordination cages that are heteroleptich as been made. This review article illustratesasystematic collection of such architectures and credible justification of their formation, along with reportedf unctional aspects of the complexes.T he collected heteroleptic assemblies are classified here into three sections:1 )[(PdL') m (L a ) x (L b ) y ]-type complexes, in which the denticity of L a and L b is equal; 2) [(PdL') m (L a ) x (L b ) y ]-type complexes, in which the denticity of L a and L b is different;a nd 3) [Pd m (L a ) x (L b ) y ]-type complexes,i n which the denticity of L a and L b is equal. Representative exampleso fs ome important homoleptic architectures are also provided, wherever possible, to set ab ackground for a better understanding of the related heteroleptic versions. The purpose of this review is to pave the way for the construction of severalu nique heteroleptic coordination assemblies that might exhibit emergents upramolecular functions.Review complexes is m + n and the total variety of components is only two. Applications of these homoleptic complexes in various fields, such as catalysis, [3] molecular recognition, [4a-c] sensing [4d] and encapsulationo fv aried guest molecules, [4c, 5] has been widely studied.Elegantarchitectures of biological multi-component systems, for example, metalloproteins and viral capsids,e xploit weak supramolecular interactions in ac ontrolled and harmonious mannerf or their construction by using relevant building blocks. [6] Occurrences of multicomponent systems in biology inspire chemistsw ho seek to advance structurala nd functional complexitieso fs upramolecular systems. Thus, in the field of metallo-supramolecular chemistry, noteworthy efforts have been directed towardt he rational design and controlled synthesis of discrete, heteroleptic structures. The methodsf or the synthesis of discrete, heteroleptic, self-assembled, coordination architectures from various metal components, such as Zn II ,F e II , Hg II ,C r III ,C o III ,R h III ,C u I ,C u II ,R u II and Pt II ,a re well explored by the groups of Lehn,F ujita, Zheng,S tang, Schm...