Nanoscale Dodecahedral and Fullerene-Type Organoboroxine and Borazine Cages from Planar Building Units.

Boroxine- and borazine-cage analogs to C20, C60, and C70 were calculated and compared in terms of structure, strain indicators, and physical properties relevant to nanoscale applications. The results show C60 and C70 type cages are less strained than the smaller congener, primarily due to minimized bending in the B-arylene-B segments. The smallest cage calculated has a diameter of 2.4 nm, which increases up to 4.9 nm by either variation of the polyhedron (C20 < C60 < C70-type cage) or organic spacer elongation between boron centers. All calculated cages are porous (apertures ranging from 0.6 to 1.9 nm). Molecular electrostatic potential and Hirshfeld population analysis revealed both nucleophilic and electrophilic sites in the interior and exterior cage surfaces. HOMO-LUMO gaps range from 3.98 to 4.89 eV and 5.10-5.18 eV for the boroxine- and borazine-cages, respectively. Our findings provide insights into the design and properties of highly porous boroxine and borazine cages for nanoscience.

A Chiral Bis-Naphthylated Tetrandrine Dibromide: Synthesis, Self-Assembly into an Organic Framework Based On Nanosized Spherical Cages, and Inclusion Studies.

Crystalline framework materials have gained interest because of their many potential applications. A novel chiral tetrandrine salt (DNT) has been synthesized and characterized by conventional analytical techniques and single-crystal X-ray diffraction analysis, and its self-assembly behavior studied. In the solid state, 48 molecules of the compound self-assemble into an organic framework based on nanospherical aggregates formed exclusively through weak noncovalent interactions. Additionally, it was demonstrated by UV-vis spectroscopy and TGA that assembled DNT can include the Nile Red dye, giving a fluorescent material. To the best of our knowledge, these spherical assemblies are the largest among the purely synthetic organic self-assembled molecular crystals reported to date.

Molecular Tectonics with Di- and Trinuclear Organotin Compounds.

Di- and trinuclear organotin(IV) complexes, in which the metal atoms are separated by large aromatic connectors, are useful building blocks for self-assembly. This is demonstrated by the preparation of [1+1], [2+2], and [2+3] macrocyclic and cage-type structures in combination with organic aromatic dicarboxylates. The linkage of the metal atoms by organic binders and the option of varying the number of reactive M-X sites generate versatile building blocks enabling molecular tectonics instead of the node-based strategy generally employed in metallo-supramolecular self-assembly.