Copper(I)-based metal-metal-to-ligand charge transfer excited state with halogen-atom transfer photo-reactivity and photocatalysis

Tang, Rui1,2; Wan, Qingyun1; Lam, Tsz-Lung1; To, Wai-Pong1; Low, Kam-Hung1; Tang, Zhou1,3; Du, Lili5; Lu, Wei2; Che, Chi-Ming1,3,4

2024-09-12

10.1016/j.chempr.2024.05.003

CHEM   影响因子和分区

2451-9294

Metal-metal-bonded excited states of Cu(I) complexes have rarely been studied, although such excited states of d (10) noble metal complexes have been well documented to cleave C-H and C-X bonds. We describe here a panel of air-stable two-coordinate binuclear Cu-2(I,I) N-heterocyclic carbene complexes with short intramolecular Cu-Cu (2.75-2.88 A & ring;) and Cu-arene (2.61-2.65 A & ring;) distances. The triplet metal-metal-to-ligand charge transfer excited states of these Cu2(I,I) 2 (I,I) complexes are highly emissive and long-lived (Phi(em) up to 0.67, T 2.9-36.1 m s in solution) and can cleave strong R-X (X = Br or Cl) bonds to give mixed-valence [X-(CuCu1.5)-Cu-1.5-Y](+/2+) (Y = X or solvent) species and carbon-centered radicals via an excited- state halogen-atom transfer mechanism. The spin-delocalized [X-(CuCu1.5)-Cu-1.5-X](+ )species (X = Br or Cl) have been characterized by single-crystal XRD, EPR spectroscopy, and density functional theory (DFT) calculations. Cu3 is an efficient photocatalyst for C-C coupling reactions with aryl/alkyl halides under 390 nm LED irradiation.

SCI

英语

其他

General Research Fund from the Hong Kong Research Grants Council[17305521] ; Guangdong Major Project of Basic and Applied Basic Research[2019B030302009] ; Key (Guangdong-Hong Kong Joint) Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province[2023B1212120011]

Chemistry

Chemistry, Multidisciplinary

WOS:001315658500001

CELL PRESS

Web of Science

1.Univ Hong Kong, Dept Chem, State Key Lab Synthet Chem, Pokfulam Rd, Hong Kong, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
3.Lab Synthet Chem & Chem Biol Ltd, Units 1503 1511, 15-F,Bldg 17W,Hong Kong Sci Pk, Hong Kong, Peoples R China
4.Chem & Chem Engn Guangdong Lab, Shantou, Guangdong, Peoples R China
5.Jiangsu Univ, Sch Life Sci, Zhejiang 212013, Peoples R China

Tang, Rui,Wan, Qingyun,Lam, Tsz-Lung,et al. Copper(I)-based metal-metal-to-ligand charge transfer excited state with halogen-atom transfer photo-reactivity and photocatalysis[J]. CHEM,2024,10(9).

Tang, Rui.,Wan, Qingyun.,Lam, Tsz-Lung.,To, Wai-Pong.,Low, Kam-Hung.,...&Che, Chi-Ming.(2024).Copper(I)-based metal-metal-to-ligand charge transfer excited state with halogen-atom transfer photo-reactivity and photocatalysis.CHEM,10(9).

Tang, Rui,et al."Copper(I)-based metal-metal-to-ligand charge transfer excited state with halogen-atom transfer photo-reactivity and photocatalysis".CHEM 10.9(2024).