Propeller-like molecules

Controlled molecular motion was achieved in several synthetic systems,including DNA machines that use a conformational change of the double helix to develop torque, and propeller-like molecules that can be rotated in a specific direction on a molecular axle by a sequence of chemical transformations. The hybridization and dissociation of DNA strands was also used to make DNA motors that extend and contract like pistons in response to DNA "fuel." One such device, unlike many artificial molecular motors, is capable of free ranning rather than requiring intervention at different points in the duty cycle. ... 

Propeller like Molecules (Several Chirality Axes)... 

Other structural concepts evolved, one of them being triptycenes (55). Here, additional wings are introduced into the molecules by Diels-Alder type reactions. The glass-forming properties are improved by the propeller-like rigid structure [89]. We end our overview of the different classes of molecular glasses with these materials and note that the number of published structures is growing every year. More details on the different materials can be found in one of the recent chemical reviews [102-104]. 

The analysis of these 25 compounds confirms the flexibility of dpg/dpg+. It can adopt a propeller like conformation and induce the formation of chiral crystals. It establishes predominantly two-dimensional H-bonding networks with the counter ion. From the perspective of the crystal engineer, an anticlinal conformation would maximize the non-linear properties of the molecule. However the non-linear optical response depends greatly on the molecular alignment. Non-centrosymmetric dispositions have not yet been achieved for dpg with an anti-anti conformation. The best strategy to attain NLO samples is by inducing a syn-anti conformation where a propeller structure might induce a chiral disposition of molecules and thus a non-centrosymmetric order. Another successful approach is to force crystallization with a chiral counterion. 

Figure 6 Singly occupied molecular orbital (SOMO) of a propeller-like trimer radical anion of acetonitrile obtained using density functional theory. The structure was immersed in a polarizable dielectric continuum with the properties of liquid acetonitrile. Several surfaces (on the right) and midplane cuts (on the left) are shown. The SOMO has a diffuse halo that envelops the whole cluster within this halo, there is a more compact kernel that has nodes at the cavity center and on the molecules.

Nonpolar and dipolar altitudinal rotors (compounds 2 and 3 in Fig. 17.3) have been synthesized. 19F NMR spectroscopy showed that the barrier to rotation in 3 was extremely low in solution. Both systems have then been immobilized on Au(l 11) surfaces and studied with a variety of techniques.57 The results obtained indicated that for a fraction of molecules the static electric field from the scanning tunneling microscopy (STM) tip could induce an orientation change in the dipolar rotor but not in the nonpolar analog (for a recent example of an azimuthal molecular rotor controlled by the STM tip, see Reference 58). Compound 3 can exist as three pairs of helical enantiomers because of the propeller-like conformation of the tetra-arylcyclobutadienes. For at least one out of the three diastereomers, an asymmetric potential energy surface can be predicted by molecular dynamics simulations on application of an alternating electric field.55... 

Sulfur extrusion is planned to yield the corresponding carbocyclic [2.2.2.2]-phanes, which are expected from regarding molecular models, to be fixed chiralilly (propeller-like). Hitherto, phane molecules containing more than four hetero bridges... 

Surprisingly, a regioselective formation of two benzoxazine rings is possible for the tetratosylates 105b, leading to molecules 110 with an overall propeller-like distortion, as shown by X-ray analysis.216... 

The bis(methylene)phosphoranes hold two carbon atoms doubly bonded to the same phosphorus atom. The molecule is chiral in the solid state due to the propeller-like orientation of the silyl groups as demonstrated in Fig. 2. 

---