Synthesis and Ion-Binding Properties of Polymeric Pseudocrown Ethers II: Template Ion Induced Cyclization of Oligomeric Ethylene Glycol Diacrylates

Abstract

Inexpensive polymeric pseudocrown ethers have been synthesized based upon a “template ion” effect in which oligomeric ethylene glycol diacrylates are induced to assume a circular conformation in which the unsaturated end-groups are in proximity. This synthetic scheme has considerable potential for the development of inexpensive materials for binding of target cations. In this contribution we report a spectroscopic study of the induced cyclization caused by ion-dipole interactions between the templating cation and the electron lone pairs of the ethylene glycol ether linkages. Fluorescence spectroscopy was used to provide insight into the templatization process by examining excimer formation in pyrene end-labeled oligomeric ethylene glycol both in the absence and in the presence of the templating ion. Pyrene end-labeled tetraethylene glycol and pentaethylene glycol were synthesized and excimer fluorescence enhancement was studied with the introduction of cations such as nickel, chromium and tin in solvents such as tetrahydrofuran and chloroform. An increase in excimer fluorescence indicated enhanced excimer formation due to the templating effect of the cation which results in the end groups being close to each other. Molecular dynamics simulations of pyrene end-labeled ligands were performed to elucidate the effect of the large fluorescent chromophores on the chain conformations.