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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...

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.

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory - Octahedral Complexes

Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...

Colors and Magnetism

Colors and Magnetism

Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...

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...

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Related Experiment Video

Updated: Jan 8, 2026

Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H2 Production in Aqueous Aerobic Conditions

Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H2 Production in Aqueous Aerobic Conditions

Published on: October 5, 2019

Dynamic Geminal-Atom Coordination for Highly Efficient Photo-Fenton Catalysis.

Yuchen Qiao¹, Su Zhan¹, Qiuchen He¹

¹Dalian Maritime University, Key Lab Ship. Machinery Maintenance & Manufacture, Ministry of Transport, Dalian, China.

Advanced Materials (Deerfield Beach, Fla.)

|December 20, 2025

Summary

Inert carbonate ions in seawater enhance a copper catalyst

Keywords:

dynamic coordinated geminal‐atom photocatalysis photo‐fenton reaction single‐atom catalysts

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[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Published on: May 21, 2019

Area of Science:

Environmental Chemistry
Catalysis
Materials Science

Background:

Geminal-atom catalysts (GACs) require modulation of active sites for improved performance.
Leveraging abundant, non-reactive environmental species is key for sustainable catalysis.

Purpose of the Study:

To develop a novel copper-based GAC.
To investigate the role of carbonate ions in seawater on catalyst activity.
To enhance photo-Fenton reactivity for marine pollutant degradation.

Main Methods:

Synthesis of a two-coordinated copper GAC.
In situ spectroscopy and control experiments.
Theoretical modeling (DFT).
Pollutant degradation assays and life-cycle assessment.

Main Results:

Carbonate ions dynamically reorganize the copper active sites.
Reversible coordination transformations modulate electronic structure and charge transfer.
A 17-fold increase in hydroxyl radical production was observed.
Efficient degradation of marine pollutants, including Chlorella, under sunlight.

Conclusions:

Carbonate ions act as activators for copper GACs in seawater.
This strategy offers mechanistic insights for designing catalysts using abundant species.
The approach is feasible for sustainable aquatic pollution remediation.