To Loop or Not to Loop: Influence of Hinge Flexibility on Self-Assembly Outcomes for Acridine-Based Triazolylpyridine Chelates with Zinc(II), Iron(II), and Copper(II)

Abstract

Coordination-driven self-assembly has been established as an effective strategy for the efficient construction of intricate architectures in both natural and artificial systems, for applications ranging from gene regulation to metal-organic frameworks. Central to these systems is the need for carefully designed organic ligands, generally with rigid components, that can undergo self-assembly with metal ions in a predictable manner. Herein, we report the synthesis and study of three novel organic ligands that feature 3,6-disubstituted acridine as a rigid spacer connected to two 2-(1,2,3-triazol-4-yl)pyridine "click" chelates through hinges of the same length but differing flexibility. The flexibility of these "three-atom" hinges was modulated by i) moving from secondary to tertiary amide functional groups and ii) replacing an sp² amide carbon with an sp³ methylene carbon. In an effort to understand the role of hinge flexibility in directing self-assembly into mononuclear loops or dinuclear cylinders, the impact of these changes on self-assembly outcomes with zinc(II), iron(II), and copper(II) ions is described.

Keywords: acridine; chelates; click chemistry; ligand design; self-assembly.