Inorganic Chemistry

Design of catalytic metal-organic assemblies via shape complementarity and conformational constraints in dual curvature ligands

Authors

Abstract

Non-covalent interactions play an essential role in the folding and self-assembly of large biological assemblies. These interactions are not only a driving force for the formation of large structures but also control conformation and com-plementary shapes of subcomponents that promote the diversity of structures and functions of the resulting assemblies. Understanding how non-covalent interactions direct self-assembly and the effect of conformation and complementary shapes on self-assembled structures will help design artificial supramolecular systems with extended components and functions. Herein, we develop a strategy for controlling more complex self-assembly with lower symmetry and flexible building blocks that combine endohedral non-covalent interactions with a dual curvature in the ligand backbone to give additional shape complementarity. A Diels-Alder reaction was used to break the symmetry of the diazaanthracene units of the ligands to give dual curvature ligands with different shapes and endohedral groups (L1-L3). The self-assembly studies of these ligands demonstrated that non-covalent interactions and shape complementary effectively control the self-assembly and enable the design of cages for supramolecular catalysis.

Version notes

Solvent optimization and additional control experiments with mononuclear Pd2+ complexes and salts were performed for the catalytic studies using the self-assembled cages. Synthesis of the control complexes and isolation/purification of the cages was added. The manuscript and the SI have been updated to include a description of these results.

Content

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Supplementary material

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Supporting Information
Complete experimental procedures, additional spectra figures, and tables of NMR, ESI-TOF-MS, CIF and crystal data.
Thumbnail image of M4-L3-UCL2062_ms_159-3EaDMF120k.cif
Pd4(L3)8
Cif file for Pd4L38
Thumbnail image of Pd2(L1)4.cif
Pd2(L1)4
cif file for Pd2(L1)4
Thumbnail image of Pd4(L2)8.cif
Pd4(L2)8
cif file for Pd4(L2)8