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Abstract Helical poly(isocyanide)s are an important class of synthetic polymers possessing a static helical structure. Since their initial discovery, numerous examples of these helices have been fabricated. In this contribution, the synthesis of a chiral, azobenzene (azo)‐containing isocyanide monomer is reported. Upon polymerization with nickel(II) catalysts, a well‐defined circular dichroism (CD) trace is obtained, corresponding to the formation of a right‐handed polymeric helix. The helical polymer, dissolved in chloroform and irradiated with UV light (365 nm), undergoes acistotransisomerization of the azobenzene side‐chains. After the isomerization, a change in conformation of the helix occurs, as evidenced by CD spectroscopy. When the solution is irradiated with LED light, the polymer returns to a right‐handed helical conformation. To open up the possibility for chain‐end post‐polymerization modification of this light‐responsive system, an alkyne‐functionalized nickel(II) catalyst is also used in the polymerization of the azobenzene monomer, resulting in a stimuli‐responsive, terminal‐alkyne‐containing helical poly(isocyanide).
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This content will become publicly available on June 27, 2026
Chirality Unbound in Graphene Nanoribbons
Abstract In this manuscript, we report the first demonstration of controlled helicity in extended graphene nanoribbons (GNRs). We present a wealth of new graphene nanoribbons that are a direct consequence of the high‐yielding and robust synthetic method revealed in this study. We created a series of defect‐free, ultralong, chiral cove‐edged graphene nanoribbons where helical twisting of the graphene nanoribbon backbone is tuned through functionalization with chiral side chains.S‐configured point chiral centers in the side chains transfer their chiral information to induce a helically chiral, right‐handed twist in the graphene nanoribbon. As the backbone is extended, these helically twisted graphene nanoribbons exhibit a substantial increase in their circular dichroic response. The longest variant synthesized consists of an average of 268 linearly fused rings, reaching 65 nm in average length with nearly 10 full end‐to‐end helical rotations. The structure exhibits an extraordinary |Δε| value of 6780 M−1cm−1at 550 nm—the highest recorded for an organic molecule in the visible wavelength range. This new chiroptic material acts as room‐temperature spin filters in thin films due to its chirality‐induced spin selectivity.
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- Award ID(s):
- 2115625
- PAR ID:
- 10614156
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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