Novel Thermotropic Liquid Crystalline and Redox-Active Complexes of Ionically Self-Assembled Poly(ferrocenylsilane) and Dendritic Amphiphiles

Abstract

A series of novel polyelectrolyte-amphiphilie complexes were prepared by ionic self-assembly of cationic linear poly(ferrocenylsilane) (PFS) of [Fe(η-C 5 H 4 ) 2 SiMe(OCH 2 CH 2 NMe 3 I)] n (PFS) with anionic dendrons of 3,4,5-tris(n-alkan-1-yloxy)benzoic acid [(3,4,5)nG1-COOK, n ) 12, 14, 16, where n was the number of carbon atoms in the alkyl tail]. These complexes PFS-(3,4,5)nG1 (n ) 12, 14, 16) were characterized with XRD, FTIR, TG, DSC, cyclic voltammetry (CV), and polarized optical microscope (POM). XRD profiles indicated the presence of the crystalline phase in the complexes resulted from the dendritic amphiphiles, which formed the end-to-end bilayer lamellar structure with the long period d ) 4.84, 5.34, and 5.76 nm for n ) 12, 14, and 16, respectively. With increasing the length of amphiphile alkyl tails, the stacking order was improved. The ionic thermotropic liquid crystalline state was obtained from these PFS-(3,4,5)nG1 complexes at temperature above the melting point of the dendron crystal. CV measurements indicated that these PFS-(3,4,5)nG1 complexes exhibited a good reversible redox process. Our work provides for the first time a simply and facile approach to fabricate redoxactive PFS polymers with ionic thermotropic liquid crystalline phase by the ionic self-assembly.

Polyferrocenylsilanes: synthesis, properties, and applications

“…28,36,68 The first of these was reported in 2000, through the treatment of poly(ferrocenylchloromethylsilane) with oligo(ethylene glycol) monomethylether or Me 2 NCH 2 CH 2 OH. 28,36,68 The first of these was reported in 2000, through the treatment of poly(ferrocenylchloromethylsilane) with oligo(ethylene glycol) monomethylether or Me 2 NCH 2 CH 2 OH.…”

“…One exception to this is atactic PFMS (PFMS: poly(ferrocenylmethylsilane)) which has Me and H substituents at silicon and was found to be semicrystalline in nature. 6,7,51,60,68,71,75,78 A significant increase in T g also occurs when the hydrogens on the cyclopentadienyl ligands are replaced with more sterically demanding alkyl groups. The presence of two melting points (87 and 102 1C) for PFMS were assigned to reorganisation of the crystals during the heating process.…”

Synthesis and Solution Self‐Assembly of Polyisoprene‐block‐poly(ferrocenylmethylsilane): A Diblock Copolymer with an Atactic but Semicrystalline Core‐Forming Metalloblock

“…27,35,67 The first of these was reported in 2000, through the treatment of poly(ferrocenylchloromethylsilane) with oligo(ethylene glycol) monomethylether or Me2NCH2CH2OH. 35 Cationic polyelectrolytes were subsequently prepared via quaternisation of the dimethylamino groups in the latter.…”

Porous Carbons – Hyperbranched Polymers – Polymer Solvation

“…Charge could be stored in the outer layers, and discharge was possible by photoinduced electron transfer [596]. Other advanced electrode modifications with ferrocene are known, e.g., liquid-crystalline ferrocene-based thin electrode films [597]. Also, electron transport via ferrocene coatings on the interior of defined pores is very dependent on the spacer between the ferrocene unit and pore wall.…”