One-Pot Self-Assembly of Stellated Metallosupramolecules from Multivalent and Complementary Terpyridine-Based Ligands.

A series of stellated metallosupramolecular architectures have been assembled through three-component integrative self-sorting. Building on the complementary ligand pairing, the initial attempts to synthesize the hexagram complex from a combination of X-shaped tetrakis- and V-shaped bis-terpyridine ligands, and CdII ions, resulted in an unprecedented mixture of stellated octanuclear and dodecanuclear metallocages, which were further isolated by column chromatography. To overcome the unexpected obstacle, the multivalent ligand design along with spontaneous heteroleptic complexation was applied to realization of the one-pot synthesis of the intricate topology. A centrally situated triangle served as a prop for quantitative formation of the six-pointed stellated complex. Notably, in the absence of the triangular prop, a four-pointed star was produced.

A Truncated Molecular Star.

A pentanuclear coordination complex assembled from any palladium(II) component and non-chelating ligands is hitherto unreported. The pentanuclear complex [Pd5 (L1)5 (L2)5 ](BF4 )10 , 1 reported here was prepared by the spontaneous complexation of [Pd(DMSO)4 ](BF4 )2 with the non-chelating bidentate ligands 1,4-phenylenebis(methylene) diisonicotinate, L1 and 4,4'-bipyridine, L2 in a one-pot method at room temperature. The planar polycyclic complex 1 with outer diameters of ≈3 nm is termed as a "molecular star" owing to its resemblance with a pentagram shape. Interim paths leading to the star were also probed to decipher related dynamics of the system.

Polyaromatic molecular peanuts.

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.

Reversible Mechanical Interlocking of D-Shaped Molecular Karabiners bearing Coordination-Bond Loaded Gates: Route to Self-Assembled [2]Catenanes.

Complexation of 1,4-phenylenebis(methylene) diisonicotinate, L1, with cis-protected Pd(II) components, [Pd(L')(NO3 )2 ], in an equimolar ratio yielded binuclear complexes, 1 a-d of [Pd2 (L')2 (L1)2 ](NO3 )4 formulation where L' stands for ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2'-bipyridine (bpy), and phenanthroline (phen). The combination of 4,4'-bipyridine, L2, with the cis-protected Pd(II) units is known to yield molecular squares, 2 a-d. However, 2 b-d coexist with the corresponding molecular triangles, 3 b-d. Combination of an equivalent each of the ligands L1 and L2 with two equivalents of cis-protected Pd(II) components in DMSO resulted in the D-shaped heteroligated complexes [Pd2 (L')2 (L1)(L2)](NO3 )4 , 4 a-d. Two units of the D-shaped complexes interlock, in a concentration dependent fashion, to form the corresponding [2]catenanes [Pd2 (L')2 (L1)(L2)]2 (NO3 )8 , 5 a-d under aqueous conditions. Crystal structures of the macrocycle [Pd2 (tmeda)2 (L1)(L2)](PF6 )4 , 4 b'', and the catenane [Pd2 (bpy)2 (L1)(L2)]2 (NO3 )8 , 5 c, provide unequivocal support for the proposed molecular architectures.