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Polycarbazole and Its Derivatives: Synthesis and Applications

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Polycarbazole and Its Derivatives: Synthesis and Applications polymers Review Polycarbazole and Its Derivatives: Synthesis and Applications. A Review of the Last 10 Years Fadila Bekkar 1, Faiza Bettahar 1, Isabel Moreno 2, Rachid Meghabar 1, Mohammed Hamadouche 3 , Estibaliz Hernáez 4, José Luis Vilas-Vilela 4,5 and Leire Ruiz-Rubio 4,5,* 1 Laboratoire de Chimie des Polymères, Université Oran1 Ahmed Ben Bella, El-Mnaouer, BP 1524, Oran 31000, Algerie; [email protected] (F.B.); [email protected] (F.B.); [email protected] (R.M.) 2 Macromolecular Chemistry Group (LQM), Organic Chemistry II Department, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), 48940 Leioa, Spain; [email protected] 3 Laboratoire de Chimie Fine, Département de Chimie, Faculté des Sciences Exactes et Appliquées, Université Oran1 Ahmed Ben Bella, El-Mnaouer, BP 1524, Oran 31000, Algerie; [email protected] 4 Macromolecular Chemistry Group (LQM), Physical Chemistry Department, Faculty of Science and Technology, University of the Basque Country (UPV/EHU), 48940 Leioa, Spain; [email protected] (E.H.); [email protected] (J.L.V.-V.) 5 BCMaterials, Basque Center for Materials, Applications and Nanostructures, UPV/EHU Science Park, 48940 Leioa, Spain * Correspondence: [email protected]; Tel.: +34-94-6017-972 Received: 20 August 2020; Accepted: 26 September 2020; Published: 28 September 2020 Abstract: Polycarbazole and its derivatives have been extensively used for the last three decades, although the interest in these materials briefly decreased. However, the increasing demand for conductive polymers for several applications such as light emitting diodes (OLEDs), capacitators or memory devices, among others, has renewed the interest in carbazole-based materials. In this review, the synthetic routes used for the development of carbazole-based polymers have been summarized, reviewing the main synthetic methodologies, namely chemical and electrochemical polymerization. In addition, the applications reported in the last decade for carbazole derivatives are analysed. The emergence of flexible and wearable electronic devices as a part of the internet of the things could be an important driving force to renew the interest on carbazole-based materials, being conductive polymers capable to respond adequately to requirement of these devices. Keywords: carbazole derivatives; conducting polymers; electropolymerization; chemical polymerization 1. Introduction Electrically conductive polymers are a highly demanded class of materials due to their extended uses in electronic and optical devices or sensors, among others. These materials present main advantageous properties of conventional polymers, such as solubility, mechanical flexibility, non-expensive fabrication or processing, with conductivity levels that could be compared to those of semiconductors or even metals. In 1977, Macdiarmid, Shirakawa and Heeger demonstrated that chemical doping of polyacetylene (PA) resulted in a highly conducting material, with its conductivity being eleven orders of magnitude higher than a pristine polymer. For this they were awarded with the Nobel Prize in 2000 for their research on conductive polymers [1,2]. These materials have induced the development of many applications, such as organic light emitting diodes (OLEDs) [3–6], organic field effect transistors (OFETs) [7–11], dye-sensitized solar cells [12–16], photochromic dyes [17–21], batteries [22–26], and electrocatalyst [27,28] or (bio)sensors [26,29–32] Polymers 2020, 12, 2227; doi:10.3390/polym12102227 www.mdpi.com/journal/polymers Polymers 2020, 12, x FOR PEER REVIEW 2 of 33 Polymers 2020, 12, x FOR PEER REVIEW 2 of 33 Polymersfield effect2020 ,transistors12, 2227 (OFETs) [7–11], dye-sensitized solar cells [12–16], photochromic dyes [17–21],2 of 33 field effect transistors (OFETs) [7–11], dye-sensitized solar cells [12–16], photochromic dyes [17–21], batteries [22–26], and electrocatalyst [27,28] or (bio)sensors [26,29–32] batteries [22–26], and electrocatalyst [27,28] or (bio)sensors [26,29–32] The term conductive polymer encompasses both organic molecules containing of alternating The term conductive polymer encompasses both organic moleculesmolecules containing of alternatingalternating simple (type σ) and double (type π) carbon bonds and/or conjugated aromatic nuclei on their simple (type(typeσ σ) and) and double double (type (typeπ) carbonπ) carbon bonds bonds and/or and/or conjugated conjugated aromatic aromatic nuclei onnuclei their skeleton.on their skeleton. This particularity, π-conjugated structure, allows the transfer of charges (electrons or holes) Thisskeleton. particularity, This particularity,π-conjugated π-conjugated structure, structure, allows the allows transfer the transfer of charges of charges (electrons (electrons or holes) or holes) along along the macromolecular skeleton. The most commonly used conjugated polymers are thealong macromolecular the macromolecular skeleton. sk Theeleton. most commonlyThe most usedcommonly conjugated used polymers conjugated are poly(thiophene)polymers are poly(thiophene) (PT) [33,34], poly(pyrrole) (PPy) [35], poly(p-phenylene) (PPP) [36], poly (p- (PT)poly(thiophene) [33,34], poly(pyrrole) (PT) [33,34], (PPy) poly(pyrrole) [35], poly(p-phenylene) (PPy) [35], poly(p-phenylene) (PPP) [36], poly (p-phenylenevinylene) (PPP) [36], poly (p- phenylenevinylene) (PPV) [37], and polyfluorene (PF) [38–41], with their structures summarized in (PPV)phenylenevinylene) [37], and polyfluorene (PPV) [37], (PF) and [38 –polyfluorene41], with their (P structuresF) [38–41], summarized with their structures in Figure1 .summarized In addition toin Figure 1. In addition to the processability inherent of many polymers, it is important to notice their theFigure processability 1. In addition inherent to the ofprocessability many polymers, inherent it is importantof many polymers, to notice theirit is important ability to modulate to notice their ability to modulate their conductivity by doping, which could vary 10from the1 isolation state (<10−10 conductivityability to modulate by doping, their which conductivity could vary by from doping the isolation, which could state( <vary10− fromS.cm the− ), isolation to the semiconductor state (<10−10 S.cm−1), to 5the semiconductor1 state (~10−5 S.cm−1), and even to4 the conductive1 material (>105 4 S.cm−11) stateS.cm− (~101), to− theS.cm semiconductor− ), and even state to the (~10 conductive−5 S.cm−1), material and even (> 10to theS.cm conductive− ) near copper material (5 (>1010 4S.cm S.cm−−1).) near copper (5 × 105 S.cm−1). Among electronic conductive polymers, polymers containing× a carbazole Amongnear copper electronic (5 × 10 conductive5 S.cm−1). Among polymers, electronic polymers conductive containing polymers, a carbazole polymers ring (PCz) containing also present a carbazole good ring (PCz) also present good electrical and optical properties. electricalring (PCz) and also optical present properties. good electrical and optical properties. Figure 1. The structure of some of the main conjugated polymers. Figure 1. The structure of some of the main conjugated polymers. Carbazole (C12HH99N),N), also also named named dibenzopyrrole or diphenylenimine,diphenylenimine, is an N-containigN-containig Carbazole (C12H9N), also named dibenzopyrrole or diphenylenimine, is an N-containig heterocyclic compound compound discovered discovered by by Graebe Graebe and and Gl Glaseraser in in1872 1872 [42]. [42 Its]. structure Its structure consists consists of two of heterocyclic compound discovered by Graebe and Glaser in 1872 [42]. Its structure consists of two twobenzene benzene ring ringfused fused on either on either side side of ofa central a central pyrro pyrrolele ring ring (Figure (Figure 2)2)[ [43].43]. Carbazole Carbazole represents represents an benzene ring fused on either side of a central pyrrole ring (Figure 2) [43]. Carbazole represents an important class of heterocycles withwith severalseveral advantages.advantages. For example, a large variety of substituents important class of heterocycles with several advantages. For example, a large variety of substituents can be easily introduced in the nitrogen atom andand the aromaticaromatic frameworkframework can be substituted in can be easily introduced in the nitrogen atom and the aromatic framework can be substituted in positions 3 andand 6,6, modifyingmodifying thethe physicochemicalphysicochemical properties.properties. Carbazol-basedCarbazol-based polymers (PCz) have positions 3 and 6, modifying the physicochemical properties. Carbazol-based polymers (PCz) have attracted increased attention over the last 50 years owing to their stability and higher redox potential attracted increased attention over the last 50 years owing to their stability and higher redox potential compared to other conducting polymers [[44].44]. Simila Similarly,rly, they present good electro-electro- andand photoactivephotoactive compared to other conducting polymers [44]. Similarly, they present good electro- and photoactive properties because of their high hole transporting mobility and strong absorption in the UV spectral properties because of their high hole transporting mobility and strong absorption in the UV spectral region [45[45].]. These These characteristics characteristics have have extended extended the use the of thisuse kindof this of polymer kind of in polymer several applications, in several region [45]. These characteristics have extended the use of this kind of polymer in several suchapplications, as transistors
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