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Impact of Positional Isomerism on Pathway Complexity in Aqueous Media
Author(s) -
Helmers Ingo,
Shen Bowen,
Kartha Kalathil K.,
Albuquerque Rodrigo Q.,
Lee Myongsoo,
Fernández Gustavo
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201911531
Subject(s) - amphiphile , hydrogen bond , aqueous solution , chemistry , self assembly , aqueous medium , functional group , nanotechnology , combinatorial chemistry , molecule , materials science , organic chemistry , polymer , copolymer
Pathway complexity has become an important topic in recent years due to its relevance in the optimization of molecular assembly processes, which typically require precise sample preparation protocols. Alternatively, competing aggregation pathways can be controlled by molecular design, which primarily rely on geometrical changes of the building blocks. However, understanding how to control pathway complexity by molecular design remains elusive and new approaches are needed. Herein, we exploit positional isomerism as a new molecular design strategy for pathway control in aqueous self‐assembly. We compare the self‐assembly of two carboxyl‐functionalized amphiphilic BODIPY dyes that solely differ in the relative position of functional groups. Placement of the carboxyl group at the 2‐position enables efficient pairwise H‐bonding interactions into a single thermodynamic species, whereas meso ‐substitution induces pathway complexity due to competing hydrophobic and hydrogen bonding interactions. Our results show the importance of positional engineering for pathway control in aqueous self‐assembly.