Alkoxy chains

Poly[2,5-dialkoxy-l,4-phenylene) vinylenejs with long solubilizing alkoxy chains dissolve in conventional organic solvents such as chloroform, toluene, or tetrahydrofuran [21, 28, 32-36]. Their emission and absorption spectra are red-shifted relative to PPV itself, and the polymers fluorescence and electroluminescence quantum yields are greater than parent PPV. This benefit may be a consequence of the long alkyl chains isolating the polymer chains from each other. 

Alkoxycarbene complexes with unsaturation in the alkyl side chain rather than the alkoxy chain underwent similar intramolecular photoreactions (Eqs. 10 and 11) [60]. Cyclopropyl carbene complexes underwent a facile vinyl-cyclopropane rearrangement, presumably from the metal-bound ketene intermediate (Eqs. 12 and 13) [61]. A cycloheptatriene carbene complex underwent a related [6+2] cycloaddition (Eq. 14) [62]. 

Lateral monofluorination of the p-alkoxyphenyl isocyanide system [XAu (CNC6H40C H2 +i)] (X = C1, Br, I), in ortho-(3-F) (6a) and meta-(2-F) (6b) positions relative to the alkoxy chain was also studied [18]. None of the free fluorinated ligands is a LC, but their gold complexes display mesomorphic properties. This is a typical case of a promesogenic ligand which yields a mesogen upon coordination to a metal. 

Given that the presence of three alkoxy chains in the phenyl group produces such a dramatic change in the properties of the material to the point that columnar mesophases are formed at room temperature, the structure of the aryl isocyanide ligand has been further modified to introduce more paraffinic chains, and examples of metallodendrimers containing monodendrons with an isocyanide group in the focal point, and its gold compound 9, have been reported [26]. 

As indicated above in chiral mesophases, the introduction of a functional group in mesogenic stmctures offers the opportunity to achieve functional LCs. With this aim, mesomorphic crown-ether-isocyanide-gold(I) complexes (26) have been prepared recently [38]. The derivatives with one alkoxy chain show monotropic SmC mesophases at or close to room temperature. In contrast, the complexes with three alkoxy chains behave as monotropic (n = 4) or enantiotropic (n > 4) LCs. The structure of the mesophases could not be fully eluddated because X-ray diffraction studies in the mesophase were unsuccessful and mesophase characterization was made only on the basis of polarized optical microscopy. These complexes are luminescent not only in the solid state and in solution, but also in the mesophase and in the isotropic liquid state at moderate temperatures. The emission spectra of 26a with n=12 were... 

Coco, S., Fernandez-Mayordomo, C., Falagan, S. and Espinet, P. (2003) Effect of alkoxy chains on the mesomorphic properties of (p-alkoxy)tetrafluoroarylgold(I) isocyanide complexes. Inorganica Chimica Acta, 350, 366-370. 

Alkoxystilbazoles can react with a variety of silver salts, AgX, to yield the two-coordinate linear complexes (19). They show liquid crystalline behavior that strongly depends on the anion, the alkoxy chain length, and other substituents which may be present on the stilbazole.59-65... 

Scheme 18. Structures of 5-alkoxyisophthalic acid 57 (C ISA, rr. number of C-atoms in the alkoxy chain), 2,5-dialkoxyterephthalic acid 58 and pyrazine 59.

Figure 9. Crystal structure of C ISA Depending on the length of the alkoxy chain, C ISA forms either cyclic hexa-mers (a C8ISA) or lamella type structures (b C ISA).

When a 7i-conjugated polymer has long alkyl or alkoxy side chains and forms the stacked structure, it tends to be aligned on the surface of substrates (e.g., Pt plate) with the alkyl or alkoxy chains oriented toward the surface of the substrate [95,128,134,135], presumably because of a strong tendency for the alkyl chain to stand upright on the surface of substrates [95,136]. Actually, the PAEs shown in No. 19 in Table 2 are aligned on a Pt plate with the OR chains oriented toward the surface of the Pt plate [95]. A model for the alignment is depicted in Fig. 1. 

Common esters such as alkyl and benzyl carboxylates are easily dealkylated by sodium hydrogen telluride, sodium telluride and sodium ditelluride in DMF. In accordance with a typical S 2 displacement at the aUcoxy group carbon, methyl, ethyl and benzyl esters react smoothly. The nucleophilicity of the reagents is enhanced by the polar aprotic solvent, and the reactivity decreases with higher alkoxy chains due to steric hindrance (e.g. 

Complexes with the simplest alkoxyphenylisocyanide and several halides are prepared by metathetical reactions of [AuCl(CNR)] with KX salts (Figure 7.19) [17]. The chloro-derivatives (n > 4) andthebromo-complexes (n > 6) display SmA phases. However, the ligands and the iodo-complexes are not liquid crystals. The transition temperatures decrease in the order Cl > Br > I, according to the decrease in polarity of the Au—X bond. It is important to note that the coordination of a very simple non-mesomorphic isocyanide (only one alkoxy chain and one aromatic ring) to Au—Cl allows the formation of a quite ordered and stable smectic mesophase. 

Figure 7.31 Three alkoxy chains cationic mesogens. A — PF6, BF4 n — 4, 8, 12.

The complexes bearing one chiral substituent display a smectic A mesophase when the non-chiral chain is long, or an enantiotropic cholesteric and a monotropic SmA phase for shorter alkoxy chains. A TGBA phase is observed for the derivative which contains the chiral isocyanide combined with the diethyloxy, when the SmA to cholesteric transition is studied. The compound with two chiral ligands shows a monotropic chiral nematic transition. When this compound is cooled very slowly from the isotropic liquid it exhibits blue phases BP-III, BP-II, and BP-I. 

Figure 7.39 (a) Schematic representation of discotic mesogens with only three alkoxy chains (n = 7, 8) (b) schematic representation of the star-shaped dimer. 

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