Bioinspired Toolkit Based on Intermolecular Encoder toward Evolutionary 4D Chiral Plasmonic Materials

Abstract

ConspectusOver the last two decades, nanophotonics, including plasmonics and metamaterials, have promised compelling opportunities for exotic control over light-matter interactions. The strong chiral light-matter interaction is a representative example. Three-dimensional (3D) chirality has existed naturally only in organic molecules and bio-organisms, but a negligible chiroptic effect was attained with these naturally occurring materials because of their small absorption cross sections. However, inspired by biological chirality, nanophotonic chiral materials have greatly expanded the design space of accessible chiroptic effects (e.g., pushing the chiral light-matter interaction to an exceptional regime, such as a broad-band circular polarizer, negative refractive index, and sensitive chiral sensing). Nevertheless, it is still a challenge to achieve precisely defined and dynamically reconfigurable chiral morphologies that further increase the chiroptic effect.Biological systems continue to inspire approaches to the design and synthesis of precisely defined 3D nanostructures. In particular, a living organism can program the evolutionary pathway of highly complexed 3D chiral morphology precisely from the molecular scale to the macroscopic scale while simultaneously enabling dynamic reconfiguration of their chirality. What if we could harness the power of biological selectivity and evolutionary capability in synthesizing chiral plasmonic materials? We envisioned that platform technology mimicking biological principles would enable control of 3D chiral structures for effective plasmonic interactions with polarized light and further impart the concept of time-dependent evolution (3D + 1D = 4D) to bring about responsive and dynamic changes in chiral plasmonics.In this Account, we review our efforts to develop the biomolecule-based synthesis of 3D chiral plasmonic materials and share the vision that as in biological systems, chirality can be programmed at the molecular level and hierarchically transferred at multiple scales to develop macroscopic chirality. Accompanied by a biomimetic time-dependent chirality of singular plasmonic nanometals, we also summarize recent achievements in the chemistry and nanophotonics communities pursuing 4D plasmonics that are closely related to our research. The biomimetic and bioinspired approaches discussed in this Account will provide new synthetic insights into implementing chiral nanomaterials and extend the range of accessible nanophotonic design. We hope that the molecular encoding approach will be useful to achieve dynamic light-matter interactions at unprecedented dimensions, time scales, and chirality. © 2019 American Chemical Society.