Mesomorphic isocyanide

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. 

Similar compounds to those shown in Figure 7.25 have been prepared with a different mesomorphic isocyanide (Figure 7.27) [15]. All of them are mesogens and exhibit short-range SmA mesophases, except the perfluorophenylpyridine derivative, which shows an SmA phase in the range 87.4-215 °C. This much longer... 

Depending on the R group, this reaction could lead to the formation of gold(I) isocyanide complexes that behave as liquid crystals. Thus, complexes [Au(C6F5) (C = N(QH4)OCioH2i-p)] and [Au(QF5)(C = N(QH4)OCnH2n + rP)] [64] where n = 4, 6, 8, 10 and 12 show this behavior. All of these complexes are mesomorphic and behave as liquid crystals showing a nematic (N) phase when the isocyanide has a... 

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. 

In summary, [Au(alkynyl)(CNR)j complexes also show mesomorphic behavior but, in contrast to the halide-isocyanide derivatives, they are thermally less stable and usually decompose before or at the clearing temperatures. This thermal instability is thought to be associated with the gold-(alkynyl) bond and makes these compounds... 

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. 

Ballesteros, B., Coco, S. and Espinet, P. (2004) Mesomorphic Mixtures of Metal Isocyanide Complexes, Induding Smectic C Mesophases at room temperature and Liquid Crystalline Molecular Alloys . Chemistry of Materials, 16, 2062-2067. 

Rod-like mononuclear derivatives have been prepared by the reaction of a polymeric alkynyl gold(I) complex with isocyanides. The mesomorphic properties of three types ofgold(I) acetylide complexes, namely, [Au(CC-Ar)(CN-Ar)J, [Au(CC-R)(CN-Ar)J and [Au(CC-Ar)(CN-R)] (Ar = aryl with aliphatic chain, R = alkyl chain), have been systematically examined. 

Liquid-crystalline gold isocyanide complexes [C H2n+iO—(CgELj)—O—C(O)—(Cg H4)—NCAuCl] react with alcohols Cmff2m+iOE[ (n = 10 or 11 m = 2 to 5) to form ZJE isomeric mixtures of carbene complexes [isomerism occurs around the C(carbene)—N bond] with mesomorphic properties and provide the first examples of liquid-crystalline metal-carbene complexes421. The isomers can also be separated, with the E form being slightly more stable than the Z form. 

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