Abstract
Chiral noble metal nanoparticles has recently gained great interest due to their potential applications including ultrasensitive chiral recognition and asymmetric synthesis. We anticipate that they could be utilized to induce asymmetric photo-polymerization reactions with high enantioselectivity and reactivity. Here, we report such a system. By employing silver nanoparticles modified with cysteine as the chiral inducer, polydiacetylene (PDA) with high chiral asymmetry was obtained from achiral diacetylene monomers triggered with unpolarized UV light. Furthermore, the helical sense of chirality can be controlled by varying the wavelength of UV irradiation. This enables a feasible and economical method to fabricate programmable 2D patterns of chiral PDA with tailored chirality distributions, such as smooth gradients in chirality and micropatterns with tailorable circularly polarized luminescence. Our finding not only opens a pathway for producing programmable chiroptical micropatterns, but also is highly valuable for deeper understanding of symmetry breaking in enantioselective photochemical reactions.
Highlights
Chiral noble metal nanoparticles has recently gained great interest due to their potential applications including ultrasensitive chiral recognition and asymmetric synthesis
We have recently shown that enantioselectivity of a photo-polymerization reaction would be elevated with superchiral light, i.e. a standing wave formed by two counterpropagating CPL20
We believe that the unusually high enantioselectivity in our system can be largely attributed to a chiral induction effect amplified by the cysteine-modified silver nanoparticles
Summary
Chiral noble metal nanoparticles has recently gained great interest due to their potential applications including ultrasensitive chiral recognition and asymmetric synthesis. We anticipate that they could be utilized to induce asymmetric photo-polymerization reactions with high enantioselectivity and reactivity. The enhanced optical asymmetry is restricted in very narrow regions near the nodes of the standing wave, making it incompatible with photopatterning[21,22] Up to date, it remains a great challenge for in situ photopatterning of such polymers with tailorable chiroptical properties in a feasible and economical fashion. The preference in handedness is dictated by geometry and configuration of the nanostructures, and the wavelength of optical excitation
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