Molecular dumbbells

Miller and co-workers have recently prepared nanometer-scaled molecular dumbbells based on poly(benzyl ether) dendrons (G1-G4) and oligoimide spacers [64], Their synthetic approach involved the coupling of amine-terminated oligoimides to dendrons with a carboxylic acid focal point. The resulting hybrid materials were found to be quite soluble thus allowing their analysis by cyclic voltammetry in DMF. Consistent with Roncali s observation, the kinetics of reduction of the oligoimide core was not found to be limited by the presence of the dendritic wedges. 

Lee M, Jeong Y-S, Cho B-K, Oh N-K, Zin W-C. Self-assembly of molecular dumbbells into organized bundles with tunable size. Chem Eur J 2002 8 876-883. 

Fig. 13 Structural analysis of the supramolecular bundles assembled from molecular dumbbells 19-21...

Fig. 13 Schematic representation of nanorings from amphiphilic molecular dumbbell 14b. Reprinted with permission from [56]. (2006) American Chemical Society...

One prominent example of rods with a soft interaction is Gay-Berne particles. Recently, elastic properties were calculated [89,90]. Using the classical Car-Parrinello scheme, the interactions between charged rods have been considered [91]. Concerning phase transitions, the sohd-fluid equihbria for hard dumbbells that interact additionally with a quadrupolar force was considered [92], as was the nematic-isotropic transition in a fluid of dipolar hard spherocylinders [93]. The influence of an additional attraction on the phase behavior of hard spherocylinders was considered by Bolhuis et al. [94]. The gelation transition typical for clays was found in a system of infinitely thin disks carrying point quadrupoles [95,96]. In confined hquid-crystalline films tilted molecular layers form near each wall [97]. Chakrabarti has found simulation evidence of critical behavior of the isotropic-nematic phase transition in a porous medium [98]. 

Figure 4.6 Relationships of idealized sd -1 -hybridized ML molecular shapes to simple polyhedra. Each panel shows the hybrid-orbital axes in dumbbell dz2 -like form embedded within the polyhedron, together with the associated allowed (no-hms-vertex) dispositions of ligands on the polyhedral vertices (with the unmarked metal atom occupying the polyhedral centroid in each case) (a) sd1 square, (b) sd2 octahedron, (c) sd3 cube, and (d) sd5 icosahedron.

For a-Ga (coordination number 1 + 2 + 2 + 2) the short Ga-Ga bond distance of 2.45 A of every Ga atom with one of its seven neighbors is characteristic, so that a-Ga is also described as a molecular metal with Ga2 dumbbells. For the low-temperature phases / -, y-, and r)-Ca the following characteristic units are observed the ladder structure (coordination number 2 + 2 + 2 + 2) for /i-gallium, Gayrings that stack to form tubes and a centered Ga wire , observed for y-Ga, and interpenetrating Gan icosahedra for b-Ga. 

Practitioners of quantum chemistry employed both the visual imagery of nineteenth-century theoretical chemists like Kekule and Crum Brown and the abstract symbolism of twentieth-century mathematical physicists like Dirac and Schrodinger. Pauling s Nature of the Chemical Bond abounded in pictures of hexagons, tetrahedrons, spheres, and dumbbells. Mulliken s 1948 memoir on the theory of molecular orbitals included a list of 120 entries for symbols and words having exact definitions and usages in the new mathematical language of quantum chemistry. 

This stiffness also has an influence on the shape of the dendrimers, when different core building units are employed. The biphenyl core 9 leads to the dumbbell shaped molecule whose most stable conformers show a twist between 20° and 60° around the central biphenyl unit. 2, based on the tetrahedral core 4, with a diabolo-like molecular shape which resembles the shape of the core very well. Due to the large number of benzene rings around the central methane unit, the branches are hindered in their rotation (Scheme 4), lowering the internal mobility of the molecule compared to 15. 

The interpretation of the Langmuir experiments with the carbosilane den-drimers is supported by the results of molecular dynamics simulation. Figure 14 shows snapshots of a dumbbell-like conformation of carbosilane dendximers observed during lateral compression of a dendrimer monolayer on a polar sub-... 

The metathesis reaction of the imine bond was also able to dynamically select for oligomers that form the most stable host-guest complex [88]. It has been shown that rodlike and dumbbell-shaped guests have a higher affinity and specificity for oligomers of 20-22 repeat units [58,61 ]. Imine starter sequences 60,61a, and 61b, which can potentially form 16- (63a), 22- (63b), and 28-mers (63c) as well as smaller molecular weight (MW) materials (62a and 62b), were chosen as starter sequences for an imine ligation experiment (Fig. 37). When equiUbrated in chloroform the product distribution of 63a-c was close to 1 1 1,... 

Figure 10.7 Probability density of die centrifuged oxygen gas as a function of the molecular angle and the free propagation time, that is, die time elapsed since die molecules have been released from die centrifuge. The white dashed line (around 1.5 ps) marks the calculated trajectory of a dumbbell distribution rotating widi die classical rotational frequency of an oxygen molecule with an angular momentum of 39ft. Part of Fig. 4 in Ref. 39.

Interestingly, the dumbbell component of a molecular shuttle exerts on the ring motion the same type of directional restriction as imposed by the protein track for linear biomolecular motors (an actin filament for myosin and a microtubule for kinesin and dynein).4 It should also be noted that interlocked molecular architectures are largely present in natural systems—for instance, DNA catenanes and rotaxanes... 

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