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. 2022 Oct 13;12(45):29187-29196.
doi: 10.1039/d2ra03265a. eCollection 2022 Oct 11.

Synthesis, electropolymerization and functionalization via click chemistry of N-alkynylated dithieno[3,2- b:2',3'- d]pyrrole

Yuriy Bandera  1   2 , Haley W Jones  1   2 , Benjamin Grant  1   2 , Sarah Mell  1   2 , Stephen H Foulger  1   2   3
Affiliations

Synthesis, electropolymerization and functionalization via click chemistry of N-alkynylated dithieno[3,2- b:2',3'- d]pyrrole

Yuriy Bandera et al. RSC Adv. .

Abstract

A new N-alkynylated dithieno[3,2-b:2',3'-d]pyrrole (DTP) monomer was synthesized using a Buchwald-Hartwig amination of 3,3'-dibromo-2,2'-bithiophene with pent-4-yn-1-amine. The obtained monomer was investigated for the possibility of a pre-polymerization modification via Huisgen 1,3-dipolar cycloaddition ("click") reaction with azide-containing organic compounds. The synthesized N-alkynylated DTP monomer is soluble in a number of organic solvents and reacts with organic azides via "click" reactions in mild conditions, achieving high yields. The N-alkynylated DTP monomer and its "click"-modified derivative can be electropolymerized to form polymeric films. Herein, the synthesis and characterization of a "click" modified DTP monomer, its pre-modified derivative, and their corresponding polymers are described. The developed method is a facile route to synthesize a new generation of various N-functionalized DTP homopolymers.

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Conflict of interest statement

There are no conflicts of interest to declare.

Figures

Scheme 1
Scheme 1. Synthesis of N-alkyl DTPs.
Scheme 2
Scheme 2. Synthesis of 5-azidopent-1-yne (1) (yield 97%), pent-4-yn-1-amine hydrochloride (2) (yield 71%), and pent-4-yn-1-amine (3) (yield 50%).
Scheme 3
Scheme 3. Synthesis of AlkyneDTP (yield 37%, 48%) and mono-aminated intermediate (4).
Scheme 4
Scheme 4. Synthesis of DTPNap (yield 81%) via 1,3-dipolar cycloaddition.
Scheme 5
Scheme 5. Polymers p-AlkyneDTP and p-DTPNap.
Fig. 1
Fig. 1. Cyclic voltammograms for the oxidation of (a) AlkyneDTP monomer (c = 2.5 mM) in acetonitrile/0.1 M TBAPF6; 1st cycle (blue) and 50th cycle (red). (b) p-AlkyneDTP; 25th cycle (blue) and 50th cycle (red). Electrolyte was acetonitrile/0.1 M TBAPF6 and scan rate was 100 mV s−1.
Fig. 2
Fig. 2. Cyclic voltammograms for the oxidation of (a) DTPNap monomer (c = 2.5 mM) in dichloromethane/0.1 M TBAPF6; 1st cycle (blue). (b) p-DTPNap; multiple cycles. Electrolyte was dichloromethane/0.1 M TBAPF6 and scan rate was 100 mV s−1.
Fig. 3
Fig. 3. Fourier transform infrared (FTIR) spectra of monomers, AlkyneDTP and DTPNap, and corresponding polymers, p-AlkyneDTP and p-DTPNap.
Fig. 4
Fig. 4. Optical absorption spectra of AlkyneDTP (blue) and DTPNap (green) monomers in dichloromethane.
Fig. 5
Fig. 5. Optical absorption spectra of (a) p-AlkyneDTP and (b) p-DTPNap in the solid state.
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