Related Experiment Video
Updated: Mar 13, 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)
[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Copper(i) 5-phenylpyrimidine-2-thiolate complexes showing unique optical properties and high visible light-directed
Meng-Juan Zhang1, Hong-Xi Li, Hai-Yan Li
1State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu, People's Republic of China. lihx@suda.edu.cn jplang@suda.edu.cn.
Abstract:
Solvothermal reactions of 5-phenylpyrimidine-2-thiol (5-phpymtH) with equimolar CuBr afforded one hexanuclear cluster [Cu6(μ3-5-phpymt)6] (1) along with a tetranuclear by-product [{(Cu2Br)(μ-5-phpymtH)}(μ3-5-phpymt)]2 (2). A two dimensional (2D) polymer [Cu4(μ5-5-phpymt)2(μ-Br)2]n (3) was isolated from the reaction of 5-phpymtH with two equiv. of CuBr. Analogous reactions of 5-phpymtH with one or four equiv. of CuI produced one tetranuclear cluster [{Cu2(μ-5-phpymtH)(μ-5-phpymt)}(μ3-I)]2 (4) and one 2D polymer [Cu6I2(μ4-I)2(μ4-5-phpymt)2]n (5). Compound 1 possesses a water-wheel-shaped hexameric structure. Compound 2 has an H-shaped tetrameric structure. Compound 3 possesses a 2D network in which unique 1D [Cu8(μ-Br)2(μ5-5-phpymt)4]n chains are connected by μ-Br- ions. Compound 4 has another tetrameric structure in which two {Cu2(μ-5-phpymtH)2(μ-5-phpymt)} fragments are linked by a pair of μ3-I- ions. Compound 5 contains another 2D network in which hexanuclear {Cu6I2(μ4-I)2} units are linked by μ4-5-phpymt bridges. The 5-phpymt ligand shows four coordination modes: μ-κ1(S)-κ1(N) (4), μ3-κ2(S)-κ1(N) (1 and 2), μ4-κ1(N)-κ2(S)-κ1(N') (5) and μ5-κ1(N)-κ3(S)-κ1(N') (3). Complex 1 shows strong solvatochromic behaviour and displays reversible luminescence switching upon alternate addition of CF3COOH and Et3N into its CHCl3 solution. Complexes 1-5 exhibit a high photocatalytic activity towards the aerobic oxidative hydroxylation of arylboronic acids to phenols under visible light irradiation. Catalyst 5 can be reused in several cycles without any obvious decay of the catalytic efficiency. These results offer an interesting insight into how the CuX/5-phpymtH molar ratios and X- ions exert great impacts on the coordination modes of the 5-phpymt- ligand, the structures of the final complexes, and the luminescence and catalytic properties.
Related Concept Videos
03:02Colors and Magnetism
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...
01:26Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
02:58Crystal Field Theory - Octahedral Complexes
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...
01:12Cycloaddition Reactions: MO Requirements for Photochemical Activation
01:32UV–Vis Spectroscopy of Conjugated Systems
One of the factors influencing λmax is the extent of conjugation in...
02:52Stereoisomerism
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...