Synthesis and electrochemical properties of redox-active [2]rotaxanes based on the inclusion complexation of 1,4-phenylenediamine and benzidine by cyclobis(paraquat-p-phenylene)

Emilio Córdova, Richard A. Bissell, Angel Kaifer

Research output: Contribution to journalArticle

77 Citations (Scopus)

Abstract

The inclusion complexation of 1,4-phenylenediamine (2) by the host cyclobis(paraquat-p-phenylene) (14+) was used as the core interaction for the template-directed synthesis of a new redox-active [2]rotaxane (54+) in high yield. The half-wave potentials for both monoelectronic oxidations of the 1,4-phenylenediamine subunit in this rotaxane exhibit remarkable anodic shifts as compared to the values typically observed in 1,4-phenylenediamine derivatives. These shifts result from the hindrance imposed by the rotaxane's tetracationic macrocyclic bead on the generation of additional positive charges. The electrostatic field created by the bead also slows down the kinetics of electron transfer, especially for the second oxidation process. Qualitatively similar effects were observed on the electrochemistry of a comparable rotaxane (74+) built around the interactions between a benzidine subunit and host 14+, but the magnitude of the effects on the voltammetric parameters was smaller than in 54+.

Original languageEnglish
Pages (from-to)1033-1038
Number of pages6
JournalThe Journal of Organic Chemistry
Volume60
Issue number4
StatePublished - Dec 1 1995

Fingerprint

Rotaxanes
Paraquat
Complexation
Electrochemical properties
Oxidation
Electrochemistry
Electric fields
Derivatives
Kinetics
4-phenylenediamine
benzidine
Oxidation-Reduction
Electrons

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

@article{73e27dcab2534388b202b542dbb9ffea,
title = "Synthesis and electrochemical properties of redox-active [2]rotaxanes based on the inclusion complexation of 1,4-phenylenediamine and benzidine by cyclobis(paraquat-p-phenylene)",
abstract = "The inclusion complexation of 1,4-phenylenediamine (2) by the host cyclobis(paraquat-p-phenylene) (14+) was used as the core interaction for the template-directed synthesis of a new redox-active [2]rotaxane (54+) in high yield. The half-wave potentials for both monoelectronic oxidations of the 1,4-phenylenediamine subunit in this rotaxane exhibit remarkable anodic shifts as compared to the values typically observed in 1,4-phenylenediamine derivatives. These shifts result from the hindrance imposed by the rotaxane's tetracationic macrocyclic bead on the generation of additional positive charges. The electrostatic field created by the bead also slows down the kinetics of electron transfer, especially for the second oxidation process. Qualitatively similar effects were observed on the electrochemistry of a comparable rotaxane (74+) built around the interactions between a benzidine subunit and host 14+, but the magnitude of the effects on the voltammetric parameters was smaller than in 54+.",
author = "Emilio C{\'o}rdova and Bissell, {Richard A.} and Angel Kaifer",
year = "1995",
month = "12",
day = "1",
language = "English",
volume = "60",
pages = "1033--1038",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Synthesis and electrochemical properties of redox-active [2]rotaxanes based on the inclusion complexation of 1,4-phenylenediamine and benzidine by cyclobis(paraquat-p-phenylene)

AU - Córdova, Emilio

AU - Bissell, Richard A.

AU - Kaifer, Angel

PY - 1995/12/1

Y1 - 1995/12/1

N2 - The inclusion complexation of 1,4-phenylenediamine (2) by the host cyclobis(paraquat-p-phenylene) (14+) was used as the core interaction for the template-directed synthesis of a new redox-active [2]rotaxane (54+) in high yield. The half-wave potentials for both monoelectronic oxidations of the 1,4-phenylenediamine subunit in this rotaxane exhibit remarkable anodic shifts as compared to the values typically observed in 1,4-phenylenediamine derivatives. These shifts result from the hindrance imposed by the rotaxane's tetracationic macrocyclic bead on the generation of additional positive charges. The electrostatic field created by the bead also slows down the kinetics of electron transfer, especially for the second oxidation process. Qualitatively similar effects were observed on the electrochemistry of a comparable rotaxane (74+) built around the interactions between a benzidine subunit and host 14+, but the magnitude of the effects on the voltammetric parameters was smaller than in 54+.

AB - The inclusion complexation of 1,4-phenylenediamine (2) by the host cyclobis(paraquat-p-phenylene) (14+) was used as the core interaction for the template-directed synthesis of a new redox-active [2]rotaxane (54+) in high yield. The half-wave potentials for both monoelectronic oxidations of the 1,4-phenylenediamine subunit in this rotaxane exhibit remarkable anodic shifts as compared to the values typically observed in 1,4-phenylenediamine derivatives. These shifts result from the hindrance imposed by the rotaxane's tetracationic macrocyclic bead on the generation of additional positive charges. The electrostatic field created by the bead also slows down the kinetics of electron transfer, especially for the second oxidation process. Qualitatively similar effects were observed on the electrochemistry of a comparable rotaxane (74+) built around the interactions between a benzidine subunit and host 14+, but the magnitude of the effects on the voltammetric parameters was smaller than in 54+.

UR - http://www.scopus.com/inward/record.url?scp=33751156895&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33751156895&partnerID=8YFLogxK

M3 - Article

VL - 60

SP - 1033

EP - 1038

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 4

ER -