Isomer-Selective Assembly of Low-Symmetry Heteroleptic Pd2LA2LB2 Cages through Coordination Sphere Engineering

27 November 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Design strategies have been developed to target the formation of structurally sophisticated coordination cages as functional hosts for various applications. These strategies include i) forming defined heteroleptic cages through integrative self-assembly of multiple ligands and ii) controlling the relative orientation of low-symmetry ligands towards specific cage isomers. The synergistic cooperation of these two approaches offers the potential for precision engineering of multi-functional, low-symmetry systems; however, it also represents a significant design challenge. In this work, by combining geometric complementarity with coordination-sphere engineering design principles, low-symmetry ligands were incorporated into heteroleptic Pd2LA2LB2-type coordination cages in an orientation-selective manner. Isomer selectivity could be fine-tuned by switching the dominant driving force between steric hindrance in the first coordination sphere and hydrogen bonding with solvent in the second coordination sphere through judicious system design. This detailed understanding of the effects of intra- and inter-molecular interactions on self-assembly outcomes provides a basis for the precision design of structurally complex assemblies beyond their primary structure.

Keywords

low-symmetry
coordination cage
coordination sphere
self-assembly
heteroleptic

Supplementary materials

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Electronic supporting information containing synthetic and analytical methods and data.
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