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Balancing Ligand Flexibility versus Rigidity for the Stepwise Self‐Assembly of M 12 L 24 via M 6 L 12 Metal–Organic Cages
Author(s) -
Liu CuiLian,
Bobylev Eduard O.,
Fu Yang,
Poole David A.,
Robeyns Koen,
Fustin CharlesAndré,
Garcia Yann,
Reek Joost N. H.,
Singleton Michael L.
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202001399
Subject(s) - covalent bond , ligand (biochemistry) , rigidity (electromagnetism) , folding (dsp implementation) , crystallography , hydrogen bond , self assembly , metal , flexibility (engineering) , materials science , chemistry , nanotechnology , molecule , receptor , mathematics , engineering , mechanical engineering , biochemistry , statistics , organic chemistry , composite material , metallurgy
Abstract Non‐covalent interactions are important for directing protein folding across multiple intermediates and can even provide access to multiple stable structures with different properties and functions. Herein, we describe an approach for mimicking this behavior in the self‐assembly of metal–organic cages. Two ligands, the bend angles of which are controlled by non‐covalent interactions and one ligand lacking the above‐mentioned interactions, were synthesized and used for self‐assembly with Pd 2+ . As these weak interactions are easily broken, the bend angles have a controlled flexibility giving access to M 2 ( L1 ) 4 , M 6 ( L2 ) 12 , and M 12 ( L2 ) 24 cages. By controlling the self‐assembly conditions this process can be directed in a stepwise fashion. Additionally, the multiple endohedral hydrogen‐bonding sites on the ligand were found to play a role in the binding and discrimination of neutral guests.