Molecular design of a "molecular syringe" mimic for metal cations using a 1,3-alternate calix[4]arene cavity

Xiaoyan Zheng, Xueye Wang*, Keqi Shen, Nuanqing Wang, Yueming Peng

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

The chemically switchable actions well imitate the function of a "molecular syringe," has been studied in theory using the 1,3-alternate calix [4]arene bearing a nitrogen-containing crown cap at one side and a bis(ethoxyethoxy) group at another side by the π-basic calixtube as a pipette and the crown ring as a rubber cap. The model is characterized by geometry optimization using density functional theory (DFT) at B3LYP/6-31G level. The obtained optimized structures are used to perform natural bond orbital (NBO) and frequency analysis. The electrondonating heteroatoms: O and N offer lone pair electrons to the contacting RY* (1-center Rydberg) or LP* (1-center valence antibond lone pair) orbitais of K+, Ag+. The results indicate that when the nitrogen atom in the crown ring is protonated, K+ and Ag+ will be pushed out to the bis(ethoxyethoxy) side through a π-basic calixtube. When the nitrogen-H + in the crown ring is deprotonated, K+ and Ag+ are sucked back to the crown-capped side again. In the course of the coordination, both the intermolecular electrostatic interactions and the cation-π interactions between the metal ion and π-orbitals of the two pairs facing inverted benzene rings play a significant role. It is believed that this prototype of a "molecular syringe" is a novel molecular architecture for the action of metal cations.

Original languageEnglish
Pages (from-to)2143-2156
Number of pages14
JournalJournal of Computational Chemistry
Volume31
Issue number11
DOIs
Publication statusPublished - Aug 2010
Externally publishedYes

Keywords

  • Calix[4]arene-N-azacrown-5
  • Density functional theory (dft)
  • Molecular syringe
  • Natural bond orbital (nbo)
  • Supramolecular chemistry

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