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Related Concept Videos

¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

2.6K
The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
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Hybridization of Atomic Orbitals II03:35

Hybridization of Atomic Orbitals II

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sp3d and sp3d 2 Hybridization
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Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

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

1.4K
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...
1.4K
Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

2.9K
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.
2.9K
Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

2.2K
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
2.2K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

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

1.6K
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...
1.6K

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Integrating a Triplet-triplet Annihilation Up-conversion System to Enhance Dye-sensitized Solar Cell Response to Sub-bandgap Light
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Interligand Coupling Drives Fast Triplet Energy Transfer Routes in PbS/Tetracene Quantum Dot Hybrids.

Benjamin Feingold1,2, Nicholas F Pompetti1, Marissa Martinez1

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ACS Nano
|November 14, 2025
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Summary

Researchers created hybrid triplet states using organic ligands and quantum dots (QDs). Ligand orientation controls electronic coupling, enabling ultrafast triplet generation for applications like photon upconversion and catalysis.

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excimerligandphotoluminescencequantum dottriplet

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Area of Science:

  • Materials Science
  • Photochemistry
  • Nanotechnology

Background:

  • Photoactive organic ligands bound to inorganic quantum dots (QDs) form hybrid architectures enabling photophysical processes.
  • Efficient triplet exciton generation using near-infrared radiation is a key process in these hybrid systems.

Purpose of the Study:

  • To report the subnanosecond generation of a hybrid triplet state with mixed ligand-QD character.
  • To investigate the influence of ligand geometry on electronic coupling and triplet energy flow.
  • To demonstrate control over ligand-QD systems for ultrafast generation of photophysically relevant species.

Main Methods:

  • Replacing native oleate ligands on small PbS QDs with 5,12-tetracenepropiolic acid.
  • Utilizing steady-state absorption, Fourier transform infrared (FTIR) spectroscopy, and density functional theory (DFT)-based geometry optimizations.
  • Analyzing photoluminescence and transient absorption to characterize intermolecular excited states.

Main Results:

  • A hybrid triplet state with mixed ligand-QD character was generated in subnanoseconds.
  • Face-on ligand geometry at low loadings led to strong electronic coupling and hastened triplet energy flow.
  • Edge-on geometry at high loadings induced intermolecular excited states with triplet excimer-like features.

Conclusions:

  • Ligand orientation on QDs can be controlled to tune electronic coupling.
  • Ultrafast generation of triplet states is achievable in ligand-QD systems.
  • These findings are valuable for applications in photon upconversion and catalysis.