Electrosynthesis and properties of poly(3,4-ethylenedioxythiophene) films functionalized with titanocene dichloride complex

Cyclic Voltammetric, Chronocoulometric, and Spectroelectrochemical Studies of Electropolymerized Films Based on (3,4-Ethylenedioxythiophene)-Substituted 3,6-Dithiophen-2-yl-2,5-dihydropyrrole[3,4-c]pyrrole-1,4-dione

“…The product was then purified by column chromatography (silica, CH 2 Cl 2 ) to give pure product in a 28% yield. 12 Ts-HMEDOT is known in the literature 15,16 but was prepared in an alternate manner by reacting tosyl chloride with hydroxymethyl EDOT in the presence of aqueous KOH in THF. 17 The characterization of DTDPP and of Ts-HMEDOT were consistent with the literature.…”

Electrosynthesis and Characterisation of Poly(3,4-Ethylenedioxythiophene) Films Incorporating Ferrocene

“…1, was the conducting polymer used in the present study in light of its several advantageous properties as compared to other polythiophene derivatives: it combines a low oxidation potential and moderate bandgap with good stability in the oxidized state, in addition to a high conductivity (> 300 S cm -1 ) [31,32]. Furthermore, both the PEDOT polymer and the metallocene used in this work (ferrocene), exhibit electrochemical response in the same potential window, allowing the modulation of the catalytic center properties [7]. In this work, we assess the benefit of the important feature of the incorporation of the supporting electrolyte ions into the polymer film during its formation, being the electrochemical properties of the polymer affected by the nature of the electrolyte employed, namely by the ferrocenium ions.…”

“…From the most noteworthy materials used for the metallic centre incorporation we can distinguish inert matrices such as silica [2] or polymeric resins [6], and electroactive supports such as electronically conducting polymers (ECPs) [7][8][9][10][11][12][13], being the latter route the approach followed in the present work. Compared with other host supports for the catalytic centres, the electrochemically prepared ECPs exhibit several advantageous characteristics such as the control of the film thickness and morphology [14] by the electrochemical mode [15][16][17][18] and conditions employed in the polymerization [19][20][21], the direct formation of the polymer in the conducting state onto a variety of substrates [22][23][24][25] and the possibility to modulate the redox state of the catalyst by electrical conditioning [5,7,26]. Moreover, being a porous material, does not restrict the catalytic activity to the film surface, allowing the access of reactants to the organometallic centres immobilized in the interior of the polymer as well as the withdraw of the reaction products to the bathing solution [26,27].…”

“…The immobilisation of such metallocomplexes in a suitable solid support presents as major advantages the fact of not having restrictions on the solubility of the catalyst, its low losses and facile separation from reaction products [5]. From the most noteworthy materials used for the metallic centre incorporation we can distinguish inert matrices such as silica [2] or polymeric resins [6], and electroactive supports such as electronically conducting polymers (ECPs) [7][8][9][10][11][12][13], being the latter route the approach followed in the present work. Compared with…”

“…Moreover, being a porous material, does not restrict the catalytic activity to the film surface, allowing the access of reactants to the organometallic centres immobilized in the interior of the polymer as well as the withdraw of the reaction products to the bathing solution [26,27]. The more effective methodology to immobilize catalytic centres inside conducting polymers consists in the electropolymerization of specially prepared funcionalized monomers [7,27]. However, this approach presents some drawbacks being the organic synthesis of the tailored monomers not the less important one.…”