Preparation and properties of rotaxanes formed by dimethyl-beta-cyclodextrin and oligo(thiophene)s with beta-cyclodextrin stoppers

Novel cyclodextrin rotaxanes with oligothiophene as an axis molecule have been prepared by the Suzuki coupling reaction of 6-O-(4-iodophenyl)-beta-CD (6-I-Ph-beta-CD) with di(1,3,2-dioxaborolan-2-yl)-oligothiophene (oligothiophene diboric ethylene glycol esters) in aqueous solutions of dimethyl-beta-cyclodextrin (DM-beta-CD). These reactions gave [2]rotaxanes and [3]rotaxanes, which were isolated by reversed phase chromatography. The fluorescence intensities of rotaxanes are higher than those of dumbbell-shaped molecules (without DM-beta-CD) in aqueous solutions. The inclusion ratio and chain length of rotaxanes have been found to relate to the emission properties and emission intensities of oligothiophene. In aqueous solutions, fluorescence quantum yields of rotaxanes are higher than those of dumbbell-shaped molecules. The increase in the fluorescence efficiency of rotaxane is caused by suppression of intermolecular interactions, indicating the effect of insulated oligothiophene with DM-beta-CD. beta-CD at the both ends of rotaxanes functions not only as bulky stoppers but also as the recognition site for guest molecules, as verified by fluorescence quenching experiments.     

Inside Cover: Self‐Assembly of One‐ and Two‐Dimensional Hemoprotein Systems by Polymerization through Heme–Heme Pocket Interactions (Angew. Chem. Int. Ed. 7/2009)

Supramolecular protein polymers consisting of cytochrome b₅₆₂ monomers with heme covalently attached to the protein surface are presented by T. Hayashi and co‐workers in their Communication on page 1271 ff. Not only one‐dimensional hemoprotein fibers with submicrometer lengths have been prepared, but when a heme triad was added as a pivot molecule, two‐dimensional protein assembly networks resulted, which cover over 100 square micrometers.

     

Reversible interpenetration in a metal-organic framework triggered by ligand removal and addition

Caging cages: Crystals of a metal-organic framework, MOF-123 [Zn(7) O(2) (NBD)(5) (DMF)(2) ] have a three-dimensional porous structure in which DMF ligands (see picture, pink) protrude into small channels. Removal of these ligands triggers the transformation of this MOF to the doubly interpenetrating form, MOF-246 [Zn(7) O(2) (NBD)(5) ]. Moreover, addition of DMF into MOF-246 triggers reverse transformation to give MOF-123. NBD=2-nitrobenzene-1,4-dicarboxylate.     

Configurational stabilization of mixed-valence states in the star-burst tetranuclear ruthenium complex bridged with acetylene links

A new tetranuclear ruthenium complex in which a metal was bridged radially to three identical metals with acetylene links showed a mixed-valence state in cyclic voltammograms. The peak potential difference for the mixed-valence state was twice the potential difference for a mixed-valence state of the corresponding binuclear complex. This fact suggests stabilization of the mixed-valence state twice by configurational modification of redox centers. However, this is inconsistent with the prediction from the additive pair model of the redox interaction. A quantum chemical model of the redox interaction was presented, in which the potential difference was expressed by the overlap integral S and the nearest neighbor interaction energy between the reduced center and the oxidized one. Application of the theory gave a negative value of S, which demonstrated reasonably the stabilization of the mixed-valence state from a quantum chemical viewpoint.