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Structural Isomerism

Structural Isomerism

Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...

Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions

Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions

Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...

Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview

Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview

Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction...

Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism

Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism

Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The alkoxide anion...

Formation of Complex Ions

Formation of Complex Ions

A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...

Valence Bond Theory

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...

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Synthetic Methodology for Asymmetric Ferrocene Derived Bio-conjugate Systems via Solid Phase Resin-based Methodology

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Published on: March 12, 2015

Anthryl-functionalized cyanide-bridged Fe/Co cubes.

Qi Liu¹, Yue Cheng¹, Shihao Liu¹

¹Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China. chenzy@sustech.edu.cn.

Dalton Transactions (Cambridge, England : 2003)

|August 29, 2023

Summary

This summary is machine-generated.

Two novel anthryl-functionalized cyanide-bridged iron-cobalt [Fe4Co4] cube complexes were synthesized. These complexes form distinct supramolecular chains and exhibit incomplete spin-crossover transitions near 200 K.

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Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production

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Published on: December 6, 2021

Area of Science:

Coordination Chemistry
Supramolecular Chemistry
Materials Science

Background:

Cyanide-bridged metal complexes offer tunable properties through variations in metal ions and ligands.
Anthracene functionalization can influence intermolecular interactions and solid-state assembly.
Spin crossover (SCO) phenomena in iron complexes are of interest for molecular switches and sensors.

Purpose of the Study:

To synthesize and characterize novel anthryl-functionalized cyanide-bridged [Fe4Co4] cube complexes.
To investigate the supramolecular assembly and magnetic properties of these complexes.
To explore the luminescence behavior and potential applications of the synthesized compounds.

Main Methods:

Synthesis and single-crystal X-ray diffraction for structural elucidation of the [Fe4Co4] cubes.
Magnetic susceptibility measurements to study spin crossover transitions.
Luminescence spectroscopy to assess photophysical properties and aggregation effects.

Main Results:

Two complexes, [(pzTp)Fe(CN)3Co(TpEtOAn)]4[OTf]4·8MeCN·7Et2O (1) and [NEt4]3[(pzTp)Fe(CN)3Co(TpEtOAn)]4[OTf]7·5MeCN·2Et2O (2), were successfully synthesized.
Complex 1 forms linear supramolecular chains via anthryl-anthryl π-π stacking, while complex 2 exhibits a zigzag 1D assembly.
Both compounds show incomplete SCO transitions from paramagnetic {FeIIILS(μ-CN)CoIIHS} to diamagnetic {FeIILS(μ-CN)CoIIILS} states around 200 K.
Complex 1 displays enhanced luminescence upon dilution or addition of perfluoronaphthalene, indicating suppression of aggregation-caused quenching (ACQ).

Conclusions:

The anthryl groups facilitate the formation of distinct supramolecular architectures in the solid state.
The [Fe4Co4] cubes exhibit temperature-dependent spin crossover behavior.
The luminescence properties suggest potential for applications where aggregation control is important, possibly related to ACQ effects.