Synthesis of Crystalline Molecular Gyrotops and Phenylene Rotation inside the Cage

Phenylene-bridged macrocage molecules were synthesized as molecular gyrotops because the rotor can rotate even in a crystal. The chain-length-dependent properties of the molecular gyrotops were investigated in order to explore the potential to create new molecular materials. The formation of the cage in the synthesis of each molecular gyrotop depended on the length of the alkyl chains of the precursor. The rotation modes and energy barriers for phenylene rotation inside the crystals of the molecular gyrotops were changed by varying the chain length of the cage

Synthesis of Crystalline Molecular Gyrotops and Phenylene Rotation inside the Cage

Phenylene-bridged macrocage molecules were synthesized as molecular gyrotops because the rotor can rotate even in a crystal. The chain-length-dependent properties of the molecular gyrotops were investigated in order to explore the potential to create new molecular materials. The formation of the cage in the synthesis of each molecular gyrotop depended on the length of the alkyl chains of the precursor. The rotation modes and energy barriers for phenylene rotation inside the crystals of the molecular gyrotops were changed by varying the chain length of the cage

Formation of Lanthanide(III)-Containing Metallosupramolecular Arrays Induced by Tris(spiroborate) Twin Bowl

Lanthanide­(III)-containing metallosupramolecular arrays were prepared in the crystalline state simply by mixing trifluoro­methane­sulfonate salts of yttrium­(III), lanthanum­(III), europium­(III), terbium­(III), erbium­(III), and ytterbium­(III) with a <i>rac</i>-tris­(spiroborate) twin bowl in <i>N</i>,<i>N</i>-dimethylformamide (DMF). In the crystal, the lanthanide­(III) ion coordinated to eight or nine DMF molecules to form spherical tricationic complexes, and the spiroborate twin bowl iteratively glued the complexes to each other to form one-dimensional arrays that were unidirectionally packed in the crystal. In each case, the array structure was stabilized by many aromatic C–H···π interactions and C–H···O hydrogen bonds between the twin bowls and the lanthanide­(III) complexes. Among the lanthanide­(III) ions, yttrium­(III), terbium­(III), erbium­(III), and ytterbium­(III) gave almost the same crystal lattice and packing, whereas a different array structure and crystal packing was observed when lanthanum­(III) and europium­(III) were used, probably due to the difference of the ionic radii of the lanthanide­(III) ions