A new terpyridine tethered polythiophene: Electrosynthesis and characterization

Abstract

A novel polythiophene bearing a pendant terpyridine moiety has been synthesized by electrochemical polymerization of a new thiophene monomer, namely 4′‐(2,2′:5′,2″‐terthien‐3′‐ethynyl)‐2,2′:6′,2″‐terpyridine (TAT). The insertion of a conjugated ethynyl spacer between the terthiophene and the terpyridine fragments provides for an effective extension of the delocalization of electrons within the structural unit and the polymer as a whole. The synthesis and characterization of the relevant monomer, the electrosynthesis of the corresponding polymer and its electrochemical, UV–visible spectroelectrochemical and IR characterization are described. Finally, a comparison between the electrochemical, spectroscopic, and spectroelectrochemical properties of PTAT and the analogue, saturated‐spacer PTTT (TTT = 4′‐[(2,2′:5′,2″‐terthien‐3′‐yl)methoxy]‐2,2′:6′,2″‐terpyridine) polymer is discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Highly Photoactive Polythiophenes Obtained by Electrochemical Synthesis from Bipyridine-Containing Terthiophenes

“…The synthetic details are reported in the Supplementary Materials (SM). The syntheses were performed by adapting literature methods [35][36][37].…”

“…The key intermediate is the 3 -bromo-2:2 ,5 :2"-terhiophene (1). Its preparation was derived from references [37,38]. The synthesis, based on a Suzuki reaction between the 2,3,5-tribromothiophene and the 2-thiopheneboronic acid, is straightforward but delicate, because a careful control of the ratio of reactants is necessary.…”

Terthiophene Appended with Terpyridine Units as Receptors for Protons and Zn2+ Ions: Photoinduced Energy and Electron Transfer Processes

“…The cyclic voltammograms of the two ligands, [8,9] performed in acetonitrile solution with tetraethylammonium hexafluorophosphate as the supporting electrolyte, exhibit a one-electron oxidation and a one-electron reduction process (Table 2), which are both chemically irreversible. In the case of TTT, the electron transfer process in the anodic region attains reversibility at scan rates higher than 5 V/s.…”

“…On the basis of the model compound TTOH and tpy, we can assign the oxidation process to the 3T moiety and the reduction process to the tpy unit: the chemical irreversibility of the observed processes precludes the comparison of the thermodynamics of the electron transfer processes. The chemical irreversibility of the oxidation process is due to the wellknown dimerization reaction of two terthiophene radical cations leading to a polymer [15] with formation of polymer films of TTT [8] and TAT [9] on the working electrode.…”

“…[4,6,7] In this paper, we report two ligands consisting of a tpy and a terthiophene unit (3T) connected by a methyleneoxy (TTT, Scheme 1) [8] and an alkynyl bridge (TAT, Scheme 1). [9] The photophysical behavior of 3Ј-hydroxymethyl-2,2Ј:5Ј,2ЈЈ-terthiophene, hereafter called TTOH, has been reported as a model of the 3T unit. The use of terthiophene instead of simple thiophene as starting compound assures more accessible potential values for electropolymerization, high regioregularity and thus high conductivity of the resulting polymer.…”