Related Experiment Video
Updated: Jan 4, 2026
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
09:12
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
9.8K
Hinged and Wide: A New P^P Ligand for Emissive [Cu(P^P)(N^N)][PF6] Complexes
Sarah Keller1,2, Matthias Bantle3, Alessandro Prescimone4
1Department of Chemistry, University of Basel, BPR 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland. sarah.keller@chimieparistech.psl.eu.
Molecules (Basel, Switzerland)
|November 6, 2019
Summary
New copper complexes with tailored bipyridine ligands exhibit yellow emission and potential for thermally activated delayed fluorescence (TADF). These findings advance the development of novel luminescent materials for optoelectronic applications.
Area of Science:
- Coordination Chemistry
- Materials Science
- Photophysics
Background:
- Heteroleptic copper complexes offer tunable electronic and photophysical properties.
- Bipyridine ligands are crucial in stabilizing copper complexes and influencing their luminescence.
Purpose of the Study:
- To synthesize and characterize novel heteroleptic copper(I) complexes featuring BIPHEP and substituted bipyridine ligands.
- To investigate the structural, electrochemical, and photoluminescent properties of these complexes.
- To explore their potential for applications in optoelectronics, particularly through thermally activated delayed fluorescence (TADF).
Main Methods:
- Synthesis of heteroleptic [Cu(BIPHEP)(N^N)][PF6] complexes.
- Characterization using multinuclear NMR spectroscopies and electrospray ionization mass spectrometry.
- Single crystal X-ray diffraction for structural determination.
- Electrochemical measurements to study Cu+/Cu2+ redox processes.
- Photoluminescence spectroscopy to determine emission wavelengths, quantum yields, and excited-state lifetimes at various temperatures.
Main Results:
- Successful synthesis and structural confirmation of four copper complexes with distorted tetrahedral coordination.
- Quasi-reversible Cu+/Cu2+ redox behavior observed for all compounds.
- Powdered samples exhibit yellow emission (λemmax 558-583 nm) with a maximum photoluminescence quantum yield (PLQY) of 14% for [Cu(BIPHEP)(5,5'-Me2bpy)][PF6].
- At 77 K, emission is red-shifted, and excited-state lifetimes increase significantly, indicating TADF in complexes with specific bipyridine ligands (6-Mebpy, 6-Etbpy, 5,5'-Me2bpy).
Conclusions:
- The synthesized copper complexes possess tunable photophysical properties, including yellow emission.
- The observed thermally activated delayed fluorescence (TADF) in select complexes opens avenues for efficient light-emitting applications.
- These findings contribute to the design of novel luminescent copper materials for advanced optoelectronic devices.
Related Concept Videos
03:02Colors and Magnetism
13.8K
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...
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...
13.8K
02:42Valence Bond Theory
11.0K
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...
11.0K
02:58Crystal Field Theory - Octahedral Complexes
30.3K
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...
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...
30.3K
02:57Coordination Number and Geometry
18.7K
For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
18.7K
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
47.8K
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
47.8K
02:51Metal-Ligand Bonds
23.7K
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...
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...
23.7K