Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 44, Pages 18755-18765Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c09595
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Funding
- Air Force Office of Scientific Research Young Investigator Program [FA9550-18-1-0159]
- 3 M Non-Tenured Faculty Award
- National Science Foundation under the Graduate Research Fellowship Program [DGE-1842165]
- NSF Centers for Chemical Innovation [CHE-1925690]
- NSF [NSF CHE-9871268]
- Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource [NSF ECCS-1542205]
- Westmont College
- State of Illinois
- International Institute for Nanotechnology
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The paper discusses a method for catalysis-free synthesis of n-type pi-conjugated polymers using photopolymerization, analyzing the mechanism behind this reaction; experimental results indicate that light excitation in the reaction facilitates monomer binding.
pi-Conjugated polymers can serve as active layers in flexible and lightweight electronics and are conventionally synthesized by transition-metal-mediated polycondensation at elevated temperatures. We recently reported a photopolymerization of electron-deficient heteroaryl Grignard monomers that enables the catalyst-free synthesis of n-type pi-conjugated polymers. Herein, we describe an experimental and computational investigation into the mechanism of this photopolymerization. Spectroscopic studies performed in situ and after quenching reveal that the propagating chain is a radical anion with halide end groups. DFT calculations for model oligomers suggest a Mg-templated SRN1-type coupling, in which Grignard monomer coordination to the radical anion chain avoids the formation of free sp(2) radicals and allows C-C bond formation with very low barriers. We find that light plays an unusual role in the reaction, photoexciting the radical anion chain to shift electron density to the termini and thus enabling productive monomer binding.
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