Multi-responsive metal–organic lantern cages in solution

Abstract

Soluble copper-based M4L4 lantern-type metal-organic cages bearing internal amines were synthesized. The solution state integrity of the paramagnetic metal-organic cages was demonstrated using NMR, DLS, MS, and AFM spectroscopy. 1D supramolecular pillars of pre-formed cages or covalent host-guest complexes selectively formed upon treatment with 4,4'-bipyridine and acetic anhydride, respectively.

Synthesis and Applications of Endohedrally Functionalized Metal‐Ligand Cage Complexes

“…As the reaction removes the OH groups from the mesocate, self‐complementary H‐bonding is no longer possible, and multiple isomers of the assembly are formed post‐reaction. Similarly, Klosterman showed N‐acylation reactions were possible through post‐assembly modification using an aniline decorated di‐Cu II paddlewheel cage . Treatment with acetic anhydride in refluxing DMF resulted in the acylation of the cage.…”

“…Similarly, Klosterman showed N-acylation reactions were possible through post-assembly modification using an aniline decorated di-Cu II paddlewheel cage. [46] Treatment with acetic anhydride in refluxing DMF resulted in the acylation of the cage. The reaction was limited to a single acylation, due to steric crowding after the first reaction.…”

Stabilizing Metal–Organic Polyhedra (MOP): Issues and Strategies

“…To evaluate their properties, these extended networks were subjected to adsorption‐based separation studies for the capture of hazardous dyes. In a related work, Klosterman and co‐workers synthesized two highly soluble copper‐based M 4 L 4 lantern‐type MOCs with free primary amine functional groups . 1D coordination polymers were constructed from the soluble cages in the presence of bridging 4,4′‐bpy linkers at room temperature over the course of one week.…”

“…In ar elated work, Klosterman and co-workerss ynthesized two highly soluble copper-based M 4 L 4 lantern-type MOCs with free primary amine functional groups. [97] 1D coordination polymers were constructed from the soluble cages in the presence of bridging 4,4'-bpy linkers at room temperature over the course of one week. These 1D chains only resulted from preformed cages, and not from a mixture of cage precursors and bridging 4,4'-bpy ligands.…”

Metal Organic Polyhedra: A Click‐and‐Clack Approach Toward Targeted Delivery

“…toward metal catalysts or harsh reaction conditions) supramolecular frameworks. [ ][ ][ ][ ] To date, only a handful examples of the PAM of MOPs have been reported . For example, Stang and co‐workers first demonstrated the use of the strain promoted alkyne‐azide click (SPAAC) [ ][ ][ ] reaction to functionalize preformed self‐assembled metallacycles.…”