Rigid spacers

The spacer rigidity of the dithioether ligand influences the resulting framework in a spectacular manner. Indeed, the unsaturated dithioether ligand l,4-bis(phenythio)butyne, including a linear alkyne -CH2-C=C-CH2- array, reacts with Cul in MeCN to afford the colorless 3D polymer... 

Aromatic polyesters constitute an important class of main-chain liquid-crystalline polymers, but present the inconvenience of their reduced solubility and very high transition temperatures (sometimes not detected before the degradation of the sample). Their processability can be improved in several ways [2,3], e.g., reduction of the rigidity of the mesogen, lengthening of the spacer, or introduction of lateral substituents. 

The sections to follow provide overviews of the more common coupling types rigid and flexible. Also discussed are couplings used for special applications floating-shaft (spacer) and fluid (hydraulic). 

A number of studies have focused on D-A systems in which D and A are either embedded in a rigid matrix [103-110] or separated by a rigid spacer with covalent bonds [111-118], Miller etal. [114, 115] gave the first experimental evidence for the bell-shape energy gap dependence in charge shift type ET reactions [114,115], Many studies have been reported on the photoinduced ET across the interfaces of some organized assemblies such as surfactant micelles [4] and vesicles [5], wherein some particular D and A species are expected to be separated by a phase boundary. However, owing to the dynamic nature of such interfacial systems, D and A are not always statically fixed at specific locations. 

Fig. 5. [3]Pseudorotaxane dendrimers from complexation of the dendrophanes and molecular rod with rigid oligo(phenylacetylene) spacers and terminal steroid units... 

Bifunctional spacer molecules of different sizes have been used to construct nanoparticle networks formed via self-assembly of arrays of metal colloid particles prepared via reductive stabilization [88,309,310]. A combination of physical methods such as TEM, XAS, ASAXS, metastable impact electron spectroscopy (MIES), and ultraviolet photoelectron spectroscopy (UPS) has revealed that the particles are interlinked through rigid spacer molecules with proton-active functional groups to bind at the active aluminium-carbon sites in the metal-organic protecting shells [88]. 

If the ligand is not directly linked to the porphyrin periphery but is held at a distance from the chromophore by a rigid spacer, more open... 

In order to determine the necessity and/or the length of the spacer that is required to achieve liquid crystalline behavior from flexible vs. rigid polymers, we have introduced mesogenic units to the backbones of a rigid [poly(2,6-dimethyl-l,4-phenylene oxide) (PPO)] and a flexible [poly(epichlorohydrin) (PECH)] polymer through spacers of from 0 to 10 methylene groups via polymer analogous reactions. 

These results demonstrate that side-chain liquid crystalline polymers can be synthesized by polymer analogous reactions from theoretically any polymer backbone. When the polymer backbone is rigid, as in the case of PPO, a long spacer is required both to decrease the Tg of the parent polymer and to partially decouple the... 

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