Stepwise Self‐Assembly and Dynamic Exchange of Supramolecular Nanocages Based on Terpridine Building Blocks

Abstract

Coordination-driven self-assembly as a powerful bottom-up approach has been extensively used to construct multifarious supramolecular architectures with increasing complexity and functionality. Due to the unique cavity structures and precisely controllable dimensions, 3D supramolecules display unprecedented properties and functions in catalysis, sensing, gas storage, and smart materials. Herein, we have built two 3D nanocages with different sizes by changing the length of the organic ligand arms. The structures were characterized by 1D and 2D NMR spectroscopy, electrospray ionization-mass spectrometry (ESI-MS), traveling wave ion mobility-mass spectrometry (TWIM-MS), gradient tandem-mass spectrometry (gMS ), and transmission electron microscopy (TEM). Furthermore, the intermolecular dynamic exchange of two 3D nanocages was conducted to construct a series of hybrid 3D structures as evidenced by mass spectrometry.

Structural studies of supramolecular complexes and assemblies by ion mobility mass spectrometry

“…Similar to the iodonium ion, the presence of (transition)metal cation can induce self‐assembly of organic ligands leading to the formation of structurally rich family of metallosupramolecular complexes. Numerous examples show the complementarity of the gas‐phase structures of metallosupramolecular systems, obtained by IM‐MS, with those observed in solution or even in the solid state revealed by NMR or X‐ray crystallography, respectively (Jiang et al, 2019; Lloyd Williams & Rijs, 2021; Sarkar et al, 2020; Wang, Liu, et al, 2018; Wang, Zhang, et al, 2018; Zhang, Wang, et al, 2018).…”

Terpyridine‐Based 3D Discrete Metallosupramolecular Architectures

“…Following this thought, two metallo‐organic tpy ligands L26 and L27 with different lengths were subsequently synthesized and two 3D nanocages ( S38 and S39 ) with the same structures were obtained by self‐assembling these two ligands with Zn(II), respectively ( Figure a). [ 97 ] Moreover, the dynamic ligand exchange behavior between these two nanocages was investigated by means of ESI‐MS and TWIM‐MS. The results underscored the versatility of these 3D supramolecular architectures in that they proved capable of tolerating different sizes of ligands with various combinations and forming hybrid self‐assembled nanocages.…”

Photocatalytic hydrogen evolution from water based on Zn–terpyridine 2D coordination nanosheets

“…† Compound 1 and Compound 2 were synthesized according to previous reports. 43,44 Then, compound 1 (2 mmol) and compound 2 (1 mmol) in 1,4-dioxane/H 2 O (14 mL/2 mL) were added in to a two-neck ask. The mixture was purged with N 2 three times.…”