Related Experiment Video
Updated: Nov 22, 2025
12:30
Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
9.4K
A hydrogen-bonded organic framework based on redox-active tri(dithiolylidene)cyclohexanetrione.
Kilingaru I Shivakumar1, Shin-Ichiro Noro, Yuna Yamaguchi
1Research Institute for Electronic Science, Hokkaido University, Sapporo, Hokkaido 001-0020, Japan. tnaka@es.hokudai.ac.jp.
Chemical Communications (Cambridge, England)
|January 7, 2021
Summary
Researchers synthesized redox-active hexakis(4-carboxyphenyl) tri(dithiolylidene)cyclohexanetrione (CPDC). This new porous framework displays permanent porosity and photoconductivity due to its unique helical hydrogen-bonding structure.
Area of Science:
- Materials Science
- Organic Chemistry
- Nanotechnology
Background:
- Development of novel porous materials is crucial for applications in energy storage and catalysis.
- Redox-active organic molecules offer tunable electronic properties for advanced material design.
Purpose of the Study:
- To synthesize a novel redox-active organic molecule, hexakis(4-carboxyphenyl) tri(dithiolylidene)cyclohexanetrione (CPDC).
- To construct and characterize a porous framework based on CPDC.
- To investigate the photophysical properties of the resulting material.
Main Methods:
- Synthesis of hexakis(4-carboxyphenyl) tri(dithiolylidene)cyclohexanetrione (CPDC) via multi-step organic reactions.
- Formation of a porous framework using CPDC through a self-assembly process driven by hydrogen bonding.
- Characterization of the framework's porosity using gas adsorption techniques.
- Evaluation of photoconductivity through electrical measurements under illumination.
Main Results:
- Successful synthesis of the redox-active CPDC molecule.
- Construction of a porous framework with permanent porosity via anomalistic helical hydrogen-bonding.
- Demonstration of significant photoconductivity in the CPDC-based porous framework.
Conclusions:
- CPDC is a promising building block for creating functional porous organic materials.
- The unique hydrogen-bonding motif enables the formation of robust porous structures.
- The observed photoconductivity opens avenues for applications in organic electronics and optoelectronics.
Related Concept Videos
01:18Aromatic Hydrocarbon Cations: Structural Overview
3.4K
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...
Removing one hydrogen from the intervening CH2 group...
3.4K
![[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
11.5K
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.
11.5K
01:26Thermal and Photochemical Electrocyclic Reactions: Overview
2.7K
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.
2.7K
01:18Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism
2.4K
Birch reduction uses solvated electrons as reducing agents. The reaction converts benzene to 1,4-cyclohexadiene. The reaction proceeds by the transfer of a single electron to the ring to form a benzene radical anion. This anion is highly basic—it abstracts a proton from the alcohol to form a cyclohexadienyl radical. Another single electron transfer gives the cyclohexadienyl anion. A proton transfer from the alcohol forms 1,4-cyclohexadiene. Since this reduction occurs via radical anion...
2.4K
01:28Stability of Conjugated Dienes
3.9K
Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
3.9K
01:17Thermal Electrocyclic Reactions: Stereochemistry
2.3K
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.
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.
2.3K