Isotope and Hydrogen‐Bond Effects on the Self‐Assembly of Macroions in Dilute Solution. Issue 71 (22nd November 2019)

• Record Type: Journal Article
• Authors: Li, Hui; Shen, Yidan; Yang, Peng; Szymanowski, Jennifer E. S.; Chen, Jiahui; Gao, Yunyi; Burns, Peter C.; Kortz, Ulrich; Liu, Tianbo
• Is Part Of: Chemistry. Volume 25:Issue 71(2019)
• Page Start: 16288
• Page End: 16293
• Publication Date: 2019-11-22
• Subjects: hydrogen bonds -- isotope effects -- macroions -- self-assembly -- solution behavior; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201902444
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: We report on the disparity in the assembly behavior of four types of nano‐sized macroions induced by isotopic substitution of protium (H) to deuterium (D) in solvents. Macroions with modest charge density can self‐assemble into single‐layer, hollow, spherical "blackberry"‐type structures, with larger assembly sizes representing stronger attractions among the macroions. Kinetically, all assembly processes become slower in D2 O than in H2 O. Thermodynamically, the polyoxometalate {SrPd12 }, the uranium cage {U60 } with alkali metal counterions, and the metal–organic cationic cage {Pd12 L24 } demonstrate similar assembly sizes in both H2 O and D2 O, whereas the metal oxide cluster {Mo72 Fe30 } as a weak acid shows an unusually large assembly size in H2 O—suggesting a stronger contribution from the hydrogen bonding in the last case. Abstract : Equal but unequal : The influence of D‐to‐H substitution in solvents onto the self‐assembly behavior of nano‐sized macroions (e.g., polyoxometalates or uranium cage) is investigated. Although showing a comparable slower self‐assemble behavior by changing the solvent, the difference in assembly sizes varies, suggesting different hydrogen‐bonding contributions within the different solvents.