Strong visible light-absorbing BODIPY-based Cu(i) cyclic trinuclear sensitizer for photocatalysis

Abstract

Exploring earth-abundant photosensitizers (PSs) with strong visible-light absorption is a long-standing interest, yet still challenging. Although copper(I) cyclic trinuclear complexes (Cu-CTCs) have exhibited fascinating photoluminescence properties, their potential application as...

Filling the gap with a bulky diaryl boron group: fluorinated and non-fluorinated copper pyrazolates fitted with a dimesityl boron moiety on the backbone

“…At 80 K, the emission lifetime of 6 elongates further to 38.9 μs. The elongated lifetime of the redshifted emission of 6 in the solid state confirms the origin is from a triplet (i.e., phosphor-Table 1 Selected bond distances (Å) and angles (°) for { [3,5- (5) and {[4-BMes 2 -3,5-(CH 3 ) 2 Pz]Cu} 3 (6), and lifetimes of photoluminescence. The Cu⋯Cu (inter) and Cu⋯Cu (intra)…”

“…Yield: 3.26 g (70%). 1 (5). Anhydrous benzene (60 mL) and acetonitrile (0.5 mL) were added to a mixture of Cu 2 O (0.22 g, 1.53 mmol) and [4-BMes 2 -3,5-(CF 3 ) 2 Pz]H (1.26 g, 2.79 mmol) in a 100 mL Schlenk flask under an inert atmosphere.…”

“…Trinuclear pyrazolates of copper represent an easily accessible and interesting category of compounds with fascinating photophysical and π-acid/π-base properties, structural features, and diverse applications. [1][2][3][4][5] For example, the d 10 copper(I) complex {[3,5-(CF 3 ) 2 Pz]Cu} 3 (1, Fig. 1) 6 reported by Dias et al, supported by a highly fluorinated pyrazolate forms columns of trimers with close Cu⋯Cu separations in crystals, and exhibits bright luminescence in the solid state and glassy solutions upon irradiation with UV radiation that can be fine-and coarse-tuned to multiple brightly visible colors by varying the solvent, concentration, temperature, and excitation wavelength.…”

“…Specifically, we report here the successful synthesis of trinuclear copper(I) complexes {[4-BMes 2 -3,5-(R) 2 Pz]Cu} 3 (Fig. 1, where R = CF 3 (5), CH 3 (6)) supported by pyrazolates bearing backbone Mes 2 B substituents and their structural and photophysical properties. (6).…”

A Photosensitizing Metal–Organic Framework as a Tandem Reaction Catalyst for Primary Alcohols from Terminal Alkenes and Alkynes

“…It was able to photosensitize O 2 to singlet oxygen ( 1 O 2 ) and superoxide anion radical (O 2 *À ), and catalyze the oxidization of organoboron. [13] Herein, we designed and synthesized a photosensitizing 2D CMOF (JNM-20, JNM = Jinan University Materials) from the Schiff-base condensation between Cu-CTU (1) and the di-aldehyde Bodipy ligand (2) (Figure 1b). Owing to strong visible-light absorption of Bodipy units and the extended π-conjugated structure, JNM-20 exhibits a wide light absorption range, excellent photoinduced charge separation efficiency, and photochemical properties.…”