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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...

¹H NMR: Interpreting Distorted and Overlapping Signals

¹H NMR: Interpreting Distorted and Overlapping Signals

Spin systems where the difference in chemical shifts of the coupled nuclei is greater than ten times J are called first-order spin systems. These nuclei are weakly coupled, and their chemical shifts and coupling constant can generally be estimated from the well-separated signals in the spectrum.
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are...

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...

Spin–Spin Coupling: One-Bond Coupling

Spin–Spin Coupling: One-Bond Coupling

Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the involved orbitals. The...

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...

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Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

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Dynamic spin filtering at the Co/Alq3 interface mediated by weakly coupled second layer molecules.

Andrea Droghetti^1,2, Philip Thielen^3,4, Ivan Rungger^1,5

¹School of Physics, AMBER and CRANN Institute, Trinity College, Dublin 2, Ireland.

Nature Communications

|September 1, 2016

Summary

This study reveals a novel spin filtering mechanism at organic-metal interfaces. It uses dynamical spin relaxation in interface states to control spin-polarized carrier injection for molecular spintronics.

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Area of Science:

Materials Science
Condensed Matter Physics
Organic Electronics

Background:

Spin filtering at organic-metal interfaces is crucial for molecular spintronics.
Interface interactions between organic molecules and magnetic electrodes dictate spin selectivity.

Purpose of the Study:

To demonstrate a new spin-filtering mechanism.
To investigate spin dynamics at Alq3/Co interfaces.
To understand the role of interface states and molecular layers in spin transport.

Main Methods:

Combined two-photon photoemission experiments and electronic structure theory.
Investigated Alq3 (tris(8-hydroxyquinolinato)aluminum) on Cobalt (Co) interfaces.
Analyzed long-time spin-dependent electron dynamics.

Main Results:

Identified a spin-filtering mechanism based on dynamical spin relaxation of interface states.
Observed that molecules in the second organic layer drive spin-dependent electron dynamics.
Interface states are not spin-split but exhibit spin-dependent lifetimes due to Co substrate interaction.

Conclusions:

Dynamical spin relaxation in interface states provides a viable spin-filtering mechanism.
This mechanism is key for spin-polarized carrier injection and diffusion in molecular spintronics devices.
The findings offer new pathways for designing advanced spintronic components.