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Thermal Electrocyclic Reactions: Stereochemistry

Thermal Electrocyclic Reactions: Stereochemistry

The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.

Thermal and Photochemical Electrocyclic Reactions: Overview

Thermal 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.

Photochemical Electrocyclic Reactions: Stereochemistry

Photochemical Electrocyclic Reactions: Stereochemistry

The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation

Metal-Ligand Bonds

Metal-Ligand Bonds

The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...

Oxidative Cleavage of Alkenes: Ozonolysis

Oxidative Cleavage of Alkenes: Ozonolysis

In ozonolysis, ozone is used to cleave a carbon–carbon double bond to form aldehydes and ketones, or carboxylic acids, depending on the work-up.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.

Oxidation-Reduction Reactions

Oxidation-Reduction Reactions

Oxidation–Reduction Reactions

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Updated: Aug 11, 2025

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Published on: April 10, 2018

Linear Conjugated Coordination Polymers for Electrocatalytic Oxygen Evolution Reaction.

Chuangye Lu^1,2, Da Zhu³, Yan Su^1,2

¹State Key Laboratory of Luminescent Materials and Devices, Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou, 510640, P. R. China.

Small (Weinheim an Der Bergstrasse, Germany)

|February 3, 2023

Summary

This summary is machine-generated.

Linear conjugated coordination polymers (LCCPs) with metal-O4 active sites show promise for the oxygen evolution reaction (OER). Cobalt-based LCCPs demonstrate superior OER performance and durability compared to commercial catalysts.

Keywords:

linear conjugated coordination polymers metal-O 4 sites oxygen evolution reaction

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Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes

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Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes

Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes

Published on: January 30, 2015

Area of Science:

Materials Science
Electrochemistry
Catalysis

Background:

Conjugated coordination polymers (CCPs) are gaining attention for energy storage and conversion.
Many CCPs have poorly defined chemical states and structures, hindering their application.
Developing CCPs with well-defined active sites is crucial for advancing catalytic processes.

Purpose of the Study:

To present linear conjugated coordination polymers (LCCPs) with metal-O4 active sites for the oxygen evolution reaction (OER).
To investigate the structure-activity relationship of LCCPs based on different metal centers (Co, Ni, Fe).
To elucidate the OER mechanism at the metal site using density functional theory (DFT).

Main Methods:

Synthesis of linear CCPs (LCCPs) with metal-O4 active sites on carbon paper.
Electrocatalytic testing for oxygen evolution reaction (OER) performance and durability.
Structural and chemical state characterization of LCCPs.
Density functional theory (DFT) calculations to understand the reaction mechanism.

Main Results:

LCCPs exhibit high crystallinity and simple structures.
The electrocatalytic activity order for OER is Co-O4 > Ni-O4 > Fe-O4.
The Co-based LCCP demonstrates superior OER performance (263 mV at 10 mA cm-2) and durability (90 h at 30 mA cm-2) compared to commercial IrO2/CP.
DFT calculations reveal the OER mechanism at the central metal site.

Conclusions:

LCCPs with metal-O4 sites are effective electrocatalysts for OER.
The Co-based LCCP offers a promising alternative to commercial catalysts.
This study provides insights into CCPs and expands their application in OER.