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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 be...

Stereoisomerism

Stereoisomerism

Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...

Radical Reactivity: Intramolecular vs Intermolecular

Radical Reactivity: Intramolecular vs Intermolecular

Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak carbon–halogen...

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

Cycloaddition Reactions: MO Requirements for Photochemical Activation

Cycloaddition Reactions: MO Requirements for Photochemical Activation

Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.

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.

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Related Experiment Video

Updated: Jun 27, 2026

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

Published on: November 29, 2018

Controlled Dimerization of Rhodium(I) Isocyanides Enables Photophysical Properties Beyond Mononuclear Complexes.

Alexander J Bukvic¹, Leander Spierling¹, Daniel Häussinger¹

¹Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland.

|June 26, 2026

Summary

This summary is machine-generated.

Researchers precisely assembled discrete dimers of photoactive metal complexes, achieving metal-metal interactions for enhanced near-infrared fluorescence and longer excited-state lifetimes. This advances polynuclear systems beyond simple mononuclear complexes.

Keywords:

aggregation luminescence metal−metal interactions pincer-ligands self-assembly

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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphos^Ph Complexes

Published on: April 10, 2015

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Last Updated: Jun 27, 2026

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

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Published on: November 29, 2018

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphos^Ph Complexes

Published on: April 10, 2015

Area of Science:

Coordination Chemistry
Supramolecular Chemistry
Photophysics

Background:

Photoactive transition metal complexes often focus on mononuclear systems.
Polynuclear architectures with metal-metal interactions offer enhanced properties but face challenges in controlled assembly.
Achieving structural precision is crucial to avoid complex mixtures and ill-defined oligomers.

Purpose of the Study:

To report the controlled assembly of discrete dimers from stacked square-planar complexes.
To explore the use of new tridentate pincer-type isocyanide ligands for precise supramolecular assembly.
To investigate how molecular design influences aggregation behavior and emergent photophysical properties.

Main Methods:

Synthesis of rhodium-(I) complexes using pincer-type isocyanide ligands with varying backbones and bite angles.
Modulation of complexes at the fourth coordination site.
Investigation of aggregation behavior influenced by pincer bite angle, auxiliary ligand, and solvent polarity.

Main Results:

Controlled assembly of discrete dimers of stacked square-planar complexes, with and without bridging ligands.
Demonstration that pincer bite angle, auxiliary ligand, and solvent polarity dictate aggregation.
Resulting dimers exhibit metal-metal interactions, leading to near-infrared fluorescence and extended triplet excited-state lifetimes compared to monomers.

Conclusions:

Precise supramolecular assembly of photoactive coordination units is achievable through rational molecular design.
Cooperative interactions in polynuclear systems can lead to emergent photophysical properties.
This work establishes design principles for developing advanced photoactive materials beyond mononuclear systems for photonic applications.