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Inversion of Optical Activity in the Synthesis of Mercury Sulfide Nanoparticles: Role of Ligand Coordination
Author(s) -
Kuno Jumpei,
Imamura Yutaka,
Katouda Michio,
Tashiro Motomichi,
Kawai Tsuyoshi,
Nakashima Takuya
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201807191
Subject(s) - chemistry , nanoparticle , denticity , ligand (biochemistry) , sulfide , carboxylate , molecule , mercury (programming language) , coordination complex , colloid , aqueous solution , inorganic chemistry , crystallography , combinatorial chemistry , photochemistry , stereochemistry , nanotechnology , organic chemistry , metal , materials science , crystal structure , biochemistry , receptor , computer science , programming language
Optical activity in inorganic colloidal materials was controlled through interactions of chiral molecules with the nanoparticle (NP) surface. An inversion of optical activity in the synthesis of mercury sulfide (HgS) NPs was demonstrated with an intrinsically chiral crystalline system in the presence of an identical chiral capping ligand. A continuous decrease in the positive first Cotton effect and an eventual reversal of CD profile were observed upon heating the aqueous solution of HgS NPs capped with N ‐acetyl‐ l ‐cysteine (Ac‐ l ‐Cys) at 80 °C. Ac‐ l ‐Cys afforded two bidentate coordination configurations with an almost mirror image of each other using the thiolate and either of carboxylate or acetyl–carbonyl groups on the HgS core. Experiment and calculation suggest that a shift in the distribution of the NP formation with energy in response to the combinations of ligand coordination structure and chiral crystalline surface is responsible for the inversion of optical activity.