Advancing
the emerging area of chiral photonics requires modeling-guided
concepts of chiral material design to enhance optical activity and
associated optical rotatory dispersion. Herein, we introduce conformational
engineering achieved by tuning polymer backbone conjugation through
introduction of thiophene structural units in a chiral fluorene polymer
backbone. Our theoretical calculations reveal a relationship between
the structural conformation and the resultant rotational strength.
We further synthesize a series of chiral fluorene-based polymers copolymerized
with thiophene whose optical chirality trend is in qualitative agreement
with predictions of our quantum chemical calculations. Varying the
number of thiophene units in the monomer building block allows us
to modulate the rotational strength by tuning the intrafibril helicity
of single-stranded polymer chains, whereby the monomer conjugation
is retained throughout the whole length of the polymer backbone. Our
design concept delineates an underexamined approach: the concept of
tuning backbone conjugation and helicity within the main chain to
enhance the optical activity of chiral polymer systems.
Designing polymeric systems with ultra‐high optical activity is instrumental in the pursuit of smart artificial chiroptical materials, including the fundamental understanding of structure/property relations. Herein, we report a diacetylene (DA) moiety flanked by chiral D‐ and L‐FF dipeptide methyl esters that exhibits efficient topochemical photopolymerization in the solid phase to furnish polydiacetylene (PDA) with desired control over the chiroptical properties. The doping of the achiral gold nanoparticles provides plasmonic interaction with the PDAs to render asymmetric shape to the circular dichroism bands. With the judicious design of the chiral amino acid ligand appended to the AuNPs, we demonstrate the first example of selective chiral amplification mediated by stereo‐structural matching of the polymer‐plasmonic AuNP hybrid pairs. Such ordered self‐assembly aided by topochemical polymerization in peptide‐tethered PDA provides a smart strategy to produce soft responsive materials for applications in chiral photonics.
Designing polymeric systems with ultra‐high optical activity is instrumental in the pursuit of smart artificial chiroptical materials, including the fundamental understanding of structure/property relations. Herein, we report a diacetylene (DA) moiety flanked by chiral D‐ and L‐FF dipeptide methyl esters that exhibits efficient topochemical photopolymerization in the solid phase to furnish polydiacetylene (PDA) with desired control over the chiroptical properties. The doping of the achiral gold nanoparticles provides plasmonic interaction with the PDAs to render asymmetric shape to the circular dichroism bands. With the judicious design of the chiral amino acid ligand appended to the AuNPs, we demonstrate the first example of selective chiral amplification mediated by stereo‐structural matching of the polymer‐plasmonic AuNP hybrid pairs. Such ordered self‐assembly aided by topochemical polymerization in peptide‐tethered PDA provides a smart strategy to produce soft responsive materials for applications in chiral photonics.
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