Donor–acceptor copolymers containing phthalazinone–thiophene structure synthesized by low-cost copper-catalyzed Ullmann polymerization

Abstract

We present a low-cost copper-catalyzed Ullmann polycondensation of phthalazinone based monomers, which provides access to polyarylethers and conjugated polymers.

Oxidative Coupling of Carbazoles: A Substituent-Governed Regioselectivity Profile

“…The starting materials, such as 3-bromo-9-( p -tolyl)-9 H -carbazole ( 3e ), carbazole ( 10a ), 3-ethyl-9 H -carbazole ( 10b ), 2-chloro-9 H -carbazole ( 10e ), and 2,7-dibromo-9 H -carbazole ( 10f ), were commercially purchased and were used as received. Other carbazoles, such as N -ethylcarbazole ( 1a ), 9-hexyl-9 H -carbazole ( 1b ), 9-decyl-9 H -carbazole ( 1c ), 9-benzyl-9 H -carbazole ( 1d ), 9-ethyl-3-methoxy-9 H -carbazole ( 1g ), 3-bromo-9-hexyl-9 H -carbazole ( 1j ), methyl 9-ethyl-9 H -carbazole-3-carboxylate ( 1k ), 9-ethyl-9 H -carbazole-3-carboxylic acid ( 1l ), 9-phenylcarbazole ( 3a ), 3,9-diphenyl-9 H -carbazole ( 3b ), 3-bromo-9-phenyl-9 H -carbazole ( 3d ), 9-( p -tolyl)-9 H -carbazole ( 3f ), 9-(1,1′-biphenyl-4-yl)-9 H -carbazole ( 3g ), 9-(4-fluorophenyl)-9 H -carbazole ( 3h ), 9-(4-bromophenyl)-9 H -carbazole ( 3j ), 9-( p -acetylphenyl)-9 H -carbazole ( 3k ), N -ethyl-2,7-dibromocarbazole ( 5c ), 2-ethoxy-9-ethyl-9 H -carbazole ( 5d ), 9-hexyl-9 H -carbazole-3-carbonitrile ( 7a ), 9-phenyl-9 H -carbazole-3-carbonitrile ( 7b ), 9-ethyl-3-nitro-9 H -carbazole ( 7c ), 3-nitro-9-phenyl-9 H -carbazole ( 7d ), 9-ethyl-3-formyl-9 H -carbazole ( 7e ), 9-hexyl-3-formyl-9 H -carbazole ( 7f ), 9-phenyl-9 H -carbazole-3-carbaldehyde ( 7g ), 3-acetyl-9-hexyl-9 H -carbazole ( 7h ), 9-ethyl-3-(dicyanovinyl)-9 H -carbazole ( 7i ), 3,6-dibromo-9-hexyl-9 H -carbazole ( 9a ), 3,6-di- tert -butyl-9-ethyl-9 H -carbazole ( 9b ), 3,6-dibromo-9-phenyl-9 H -carbazole ( 9c ), 3-(biphenyl-2-yl)-6-bromo-9-phenyl - 9 H -carbazole ( 9d ), 9-acetyl-9 H -carbazole ( 9e ), 3,6-dibromo-9 H -carbazole ( 10c ), and 2-( tert -butyl)-9 H -carbazole ( 10d ) were synthesized according to the literature reported procedures and characterized by 1 H and 13 C NMR spectroscopy, and the data were verified with the cited literature reports. − …”

Advances in the application of named reactions in polymer synthesis

“…Ming Li’s large-scale preparation of C 3 N 3 from inexpensive cyanuric chloride on copper surfaces based on Ullmann polymerization under non-vacuum conditions has good water-splitting photoelectrochemical (PEC) activity and can be exfoliated into 2D polymer films (Figure 20(b)). 121 This groundbreaking work not only expands the PCN family, but also opens the door for the large-scale synthesis of other similar C-C-bonded 2D conjugated polymers.

Figure 20.(a) The synthetic route to the donor–acceptor copolymers 118,120 ; (b) polymerization of C 3 N 3 C 3 on copper foil. 121

…”

“…118 In fact, the ullmann reaction has an irreplaceable position in polymer synthesis on account of the availability of its monomers compared with other common metal-catalyzed cross-couplings and the uniqueness of functional group transformations that it can achieve. 119 Jinyan Wang et al 118 , 120 proposed an efficient method to synthesize Donor-Acceptor (D-A) polymers via classical Ullmann coupling polymerization based on monomers containing both OH and NH groups, which provides access to polyarylethers and conjugated polymers (Figure 20(a)), The number-average molecular weight of polymers can even reach 17.9 kDa. Ullmann reaction also led to a breakthrough in the synthesis of the polymer carbon nitride (PCN), C 3 N 3 has been previously predicted but has not yet been successfully synthesized before.…”

Contemporary Approaches for Conventional and Light‐Mediated Synthesis of Conjugated Heteroaromatic Polymers

“…Contrary to Pd catalysts, copper can bind to many N/O ligands and Ullmann reaction has tolerance to the most of the functional groups (Scheme 3). [70,71] New strategies involve the use of metal nanoparticles (mainly CuNPs and AgNPs) which are 10 5 times cheaper than Pd-catalysts, and they show much higher catalytic activity (Scheme 4). [72] It is also possible to support the metal NPs to the organic structures such as cellulose to accomplish homogenous conditions for shorter reaction times.…”

“…Synthesis of 2D polythiophene derivatives using AgNPs. [70] Scheme 5. Synthesis of carbazole-based conjugated polymer using Ullmann coupling polymerization.…”