Electroactive Polymeric Networks Created by Oxidation of Oligothiophene‐Functionalized Perylene Bisimides

Abstract

A series of fourfold oligothienyl‐functionalized perylene bisimides, N,N′‐bis(2,6‐diisopropylphenyl)‐1,6,7,12‐tetra(4‐(7‐[2,2′]bithien‐5‐yl)‐heptanoyloxyphenoxy)perylene‐3,4:9,10‐tetracarboxylic acid bisimide (7a), N,N′‐bis(2,6‐diisopropylphenyl)‐1,6,7,12‐tetra(4‐(7‐[2,2′;5′,2′′]terthien‐5‐yl)‐heptanoyloxyphenoxy)perylene‐3,4:9,10‐tetracarboxylic acid bisimide (7b), and N,N′‐bis(2,6‐diisopropylphenyl)‐1,6,7,12‐tetra(4‐(7‐(5″‐Methyl‐[2,2′;5′,2″]terthien‐5‐yl))‐heptanoyloxyphenoxy)perylene‐3,4:9,10‐tetracarboxylic acid bisimide (7c), have been synthesized. Oligothienyl and perylene bisimide chromophores in these dyads display their characteristic optical UV/vis absorption properties. Upon excitation of the oligothiophene subunits, fluorescence resonance energy transfer (FRET) occurs to the perylene bisimide core. Cyclic voltammetric studies revealed that the reduction of the perylene bisimide moiety is not affected by the presence of oligothiophenes, showing two waves at around ‐0.7 and ‐1.0 V versus Ag/AgCl, respectively. On the other hand, the oxidation of the oligothienyl moieties leads to oxidative coupling for 7a and 7b, providing electroactive sexithiophene‐ and quaterthiophene‐perylene bisimide networks, respectively. Electrochemical deposition of compounds 7a,b was performed and the films were characterized using cyclic voltammetry and in situ conductance, which reveal remarkable p‐type conductivity. Significantly, two separate regimes of electrical conductance have been observed for the films generated from 7b.

Structure–charge transfer property relationship in self-assembled discotic liquid-crystalline donor–acceptor dyad and triad thin films

“…Compared to most of liquid-crystalline D-A dyads/triads reported so far, [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] the spacing between the discotic D and A units controlled by the aliphatic periphery is larger in the present molecular architecture. On the one hand, small spacing is generally preferred in order to ensure the fast and efficient formation of photoinduced CT states.…”

“…Among the variety of LC donor-acceptor (D-A) materials developed so far, [25][26][27][28] covalently linked electron D-A dyad and triad molecules are of interest as their self-assembly can produce highly ordered wellseparated structures of well-stacked D and A p-molecules. [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] In such supramolecular systems, excitons are photogenerated close to the D-A interface and pathways for hole and electron transport are well dened, providing a suitable conguration for efficient formation of excited charge transfer (CT) states and ambipolar charge transport. While the power conversion efficiency of organic solar cells based on a LC nematic donor material blended with a fullerene derivative has recently reached 9.3%, 47 the highest efficiency reported in devices based on D-A liquid crystals is about 2.7%.…”

Analysis of Conjugated Polymers Conductivity by in situ Electrochemical‐Conductance Method

“…In recent years using this technique, different polymer films derived from polyfurans, PTh, PPy, PANI, polyalcoxythiophenes to organometallics polymers, dendrimer structures and conjugated radical polymers, have been examined. [81,[92][93][94][95][96][97][98][99][100][101][102][103][104][105][106][107][108][109][110] Conductance behavior, charge/discharge process, n-doping and charge trapping are the most common phenomena studied. Commonly these studies have been carried out using low scan rate values (v � 10 mV s À 1 ) in order to obtain reliable data, because some structural changes during the charge/discharge process are slow and using higher scan rates unreproducible data could be obtained.…”

Conducting Polymer Networks Cross‐Linked by “Isolated” Functional Dyes: Design, Synthesis, and Electrochemical Polymerization of Doubly Strapped Light‐Harvesting Porphyrin/Oligothiophene Monomers

“…In addition, when these two components are conjugated in such a way that some chemical stimuli (i.e., analytes) can perturb the electronic interactions between them, the integrated materials function as chemosensors. [37,38] Thus, conducting polymers functionalized with photo-and electroactive molecules, mostly p-conjugated molecules, such as porphyrins, [14][15][16][17][18][19] phthalocyanines, [20,21] perylenes, [22][23][24][25] fullerenes, [26][27][28] and so forth, [29][30][31][32][33][34][35][36] have been reported. A recent example reported by Würthner and co-workers showed that oligothiophenefunctionalized perylene bisA C H T U N G T R E N N U N G (imide)s yield polymeric networks that consist of alternating p-and n-type materials at the molecular level.…”

“…A recent example reported by Würthner and co-workers showed that oligothiophenefunctionalized perylene bisA C H T U N G T R E N N U N G (imide)s yield polymeric networks that consist of alternating p-and n-type materials at the molecular level. [22,23] Swager and co-workers reported that a porphyrin-incorporated polythiophene network structure acts as a highly sensitive conductometric fluoride ion sensor. [17] In these functionalized polymeric materials, not only the control of the electronic interaction between the polymer backbone and the incorporated functional molecule but also the prevention of self-aggregation of these p-conjugated systems is of importance.…”