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Recent developments in the synthesis of regioregular thiophene-based conjugated polymers for electronic and optoelectronic applications using nickel and palladium-based catalytic systems
Authors:Bibi Amna  Humaira Masood Siddiqi  Abbas Hassan  Turan Ozturk
Institution:Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 Pakistan ; Istanbul Technical University, Department of Chemistry, 34469 Maslak Istanbul Turkey.; TUBITAK-UME, Chemistry Group of Laboratories, PO Box 54, Gebze Kocaeli 41471 Turkey
Abstract:Thiophene-based conjugated polymers hold an irreplaceable position among the continuously growing plethora of conjugated polymers due to their exceptional optical and conductive properties, which has made them a centre of attention for the past few decades and many researchers have contributed tremendously by designing novel strategies to reach more efficient materials for electronic applications. This review aims to highlight the recent (2012–2019) findings in design and synthesis of novel thiophene-based conjugated polymers for optical and electronic devices using organometallic polycondensation strategies. Nickel- and palladium-based protocols are the main focus of this account. Among them nickel-catalyzed Kumada catalyst-transfer polycondensation, nickel-catalyzed deprotonative cross-coupling polycondensation, palladium-catalyzed Suzuki–Miyaura and Migita–Kosugi–Stille couplings are the most popular strategies known so far for the synthesis of functionalized regioregular polythiophenes exhibiting fascinating properties such as electronic, optoelectronic, chemosensitivity, liquid crystallinity and high conductivity. This account also presents a brief overview of direct arylation polymerization (DArP) protocol that has shown a great potential to lessen the drawbacks of conventional polymerization techniques. DArP is a cost-effective and green method as it circumvents the need for the synthesis of arylene diboronic acid/diboronic ester and distannyl arylenes using toxic precursors. DArP also puts off the need to preactivate the C–H bonds, hence, presenting a facile route to synthesize polymers with controlled molecular weight, low polydispersity index, high regioregularity and tunable optoelectronic properties using palladium-based catalytic systems.

Thiophene-based conjugated polymers are important conjugated polymers due to their exceptional optical and conductive properties, over the past few decades many researchers have designed novel strategies to reach more efficient materials for electronic applications.
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