Related Experiment Video
Updated: May 18, 2026
![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
09:12
[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Pseudorotaxane based on tetraazamacrocyclic copper complex and dibenzocrown ether.
Joanna Małecka1, Iwona Mames, Mateusz Woźny
1Faculty of Chemistry, University of Warsaw, Pasteura 1, 02093 Warsaw, Poland.
Dalton Transactions (Cambridge, England : 2003)
|September 6, 2012
Summary
Host-guest interactions between dibenzocrown ethers and copper complexes form pseudorotaxanes. Stronger interactions were observed with copper(III) and larger crown ethers, impacting electrode properties.
Area of Science:
- Supramolecular Chemistry
- Electrochemistry
- Materials Science
Background:
- Host-guest chemistry involves interactions between molecular receptors (host) and substrates (guest).
- Macrocyclic complexes, like copper tetraimine, offer unique structural and electronic properties for host-guest studies.
- Dibenzocrown ethers are electron-rich macrocycles capable of forming complexes with various cations.
Purpose of the Study:
- To investigate host-guest interactions between dibenzocrown ethers and copper tetraimine complexes.
- To explore the influence of copper oxidation state and crown ether size on complex formation.
- To examine the self-assembly of copper complexes on gold surfaces and their subsequent interactions with crown ethers.
Main Methods:
- Solution-state studies using Nuclear Magnetic Resonance (NMR) spectroscopy.
- Electrochemical techniques including cyclic voltammetry.
- Surface assembly of thiolated copper complexes on gold electrodes.
Main Results:
- Formation of pseudorotaxanes in solution through host-guest interactions.
- Enhanced complexation observed with copper(III) compared to copper(II) complexes.
- Stronger binding affinity of larger (30-membered) dibenzocrown ethers with copper complexes.
- Self-assembled monolayers of copper complexes on gold electrodes exhibited electroactivity.
- Donor-acceptor interactions at the electrode surface modulated electron transfer and barrier properties.
Conclusions:
- Dibenzocrown ethers and copper tetraimine complexes form stable pseudorotaxanes.
- Electrochemical and structural factors significantly influence host-guest complexation.
- Surface-confined copper complexes can interact with crown ethers, altering interfacial electronic properties.
More Related Videos
Related Concept Videos
01:18Aromatic Hydrocarbon Cations: Structural Overview
Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group with both...
Removing one hydrogen from the intervening CH2 group with both...
01:26Thermal and Photochemical Electrocyclic Reactions: Overview
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
02:37Disubstituted Cyclohexanes: cis-trans Isomerism
Depending upon the different spatial orientation of the substituents, the disubstituted cycloalkanes exhibit two types of stereoisomers. The cis isomers have the substituents on the same side of the ring, whereas the trans isomers have the substituents on the opposite sides. These stereoisomers exhibit different physical properties and cannot be interconverted without breaking the carbon-carbon bonds.
In cyclohexane, the substituents can occupy different positions generating distinct isomers.
In cyclohexane, the substituents can occupy different positions generating distinct isomers.
![[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2Ffiles%2Fmedia%2Fscience-education%2Fscience-education-thumbs%2F12417.jpg&w=3840&q=75)
01:16[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
02:36Crown Ethers
Crown ethers are cyclic polyethers that contain multiple oxygen atoms, usually arranged in a regular pattern. The first crown ether was synthesized by Charles Pederson while working at DuPont in 1967. For this work, Pedersen was co-awarded the 1987 Nobel Prize in Chemistry. Crown ethers are named using the formula x-crown-y, where x is the total number of atoms in the ring and y is the number of ether oxygen atoms. The term 'crown' refers to the crown-like shape that these ether molecules take.
01:27Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).