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Self-association and columnar liquid crystalline phase of cationic alkyl-substituted-bipyridine benzenedithiolato gold(iii) complexes.
- Source :
- Dalton Transactions: An International Journal of Inorganic Chemistry; 2013, Vol. 42 Issue 45, p15995-16005, 11p
- Publication Year :
- 2013
-
Abstract
- The introduction of a Au(iii) ion into a mesogenic core, [M(Bdt)(Cnbpy)]<superscript>+</superscript> (Bdt = 1,2-benzenedithiolato and Cnbpy = 4,4′-di-alkyl-2,2′-bipyridine (n = 13 (4,4′-di-tridecyl-2,2′-bipyridine (C13bpy)) and 8,10 (4,4′-di-(3-octyltridecyl)-2,2′-bipyridine (C8,10bpy)))), leads to the formation of ionic molecular assemblies in crystalline and mesophases. Successive syntheses of precursor complexes, [AuCl<subscript>2</subscript>(Cnbpy)]PF<subscript>6</subscript> (n = 13 (1) and 8,10 (2)), followed by the target complexes, [Au(Bdt)(Cnbpy)]PF<subscript>6</subscript> (n = 13 (3) and 8,10 (4)), were achieved. The crystallographic analysis of 3 revealed that the central cationic cores form a characteristic one-dimensional columnar structure, which is an essential property for the formation of columnar structures in the liquid crystalline phase. The central cores of the [Au(Bdt)(C13bpy)]<superscript>+</superscript> cations in 3 stack alternatively so as to cancel out their dipole moments and the counteranions lie between the cationic columns. Furthermore, the introduction of the branched alkyl tails in 4 induces the formation of a rectangular columnar liquid crystalline phase (Col<subscript>r</subscript>) with C2/m symmetry, and it melts to an isotropic liquid at 69 °C. The Col<subscript>r</subscript> phase of 4 is partially similar in its liquid crystalline structure to the neutral [Pt(Bdt)(C8,10bpy)] liquid crystal in a hexagonal columnar phase reported previously, while complex 4 shows a lower clearing point than that of the Pt analogue. Based on these results, the present study demonstrates the designability of the liquid crystalline structures of the [M(Bdt)(C8,10bpy)] skeleton together with their assembled structures and physico-chemical properties. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 42
- Issue :
- 45
- Database :
- Complementary Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 100893322
- Full Text :
- https://doi.org/10.1039/c3dt51444g