Perylene diimide covalent organic frameworks super-reductant for visible light-driven reduction of aryl halides

doi:10.1016/S1872-2067(23)64592-9

Abstract

Abstract:

In recent years, there has been a growing interest in the utilization of molecular photocatalysts in their radical ionic forms, especially as visible-light super-reductants. These catalysts exhibit remarkable capabilities in facilitating otherwise inert high-potential organic reactions, such as the reduction of aryl halides to aryl radicals. However, the development of heterogeneous super-reductants has lagged behind due to the deactivation effect caused by molecular aggregation. This study presents a novel approach to address this limitation by heterogenizing perylene diimides (PDIs) super-reductants with a consecutive photo-induced electron transfer mechanism into two-dimensional donor-acceptor (D-A) covalent organic frameworks (COFs). Both COFs, possessing D-A electronic structures and photothermal effects, demonstrated superior visible-light photocatalytic performance compared to their homogeneous counterparts. They achieved up to 99% conversion in the dehalogenation of aryl halides, primarily through a hydrogen atom trapping aryl radical mechanism. Additionally, we conducted a comparative investigation of the excited states of radical anionic D-A-type COFs and DPPDI using femtosecond transient absorption spectroscopy. Notably, the lifetimes of COFs were significantly prolonged, measuring 210 and 260 ps, respectively, compared to the 150 ps lifetime of (DPPDI^•−). This study offers valuable insights into the design of efficient free radical ion-type photocatalysts, with potential applications in various chemical transformations.

Key words: Perylene diimide, Covalent organic frameworks, Photocatalyst, Homogeneous, Reduction of aryl halides

Yucheng Jin, Xiaolin Liu, Chen Qu, Changjun Li, Hailong Wang, Xiaoning Zhan, Xinyi Cao, Xiaofeng Li, Baoqiu Yu, Qi Zhang, Dongdong Qi, Jianzhuang Jiang. Perylene diimide covalent organic frameworks super-reductant for visible light-driven reduction of aryl halides[J]. Chinese Journal of Catalysis, 2024, 57: 171-183.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64592-9

https://www.cjcatal.com/EN/Y2024/V57/I2/171

Figures/Tables 7

Scheme 1. Synthesis of USTB-21 and USTB-22.

Scheme 2. Chemical synthesis of the TFPDI.

Fig. 1. PXRD data of USTB-21 (a) and USTB-22 (b) (experimental PXRD profile (black), refined profile (red), the difference between the experimental and refined PXRD (gray), and simulation pattern (cyan)). The simulated AA stacking structures of USTB-21 (c,d) and AB stacking structures of USTB-22 (e,f). SEM (g), TEM (h), and HRTEM (i,j) images of USTB-21. SEM (k), TEM (l), and HRTEM (m,n) images of USTB-22.

Fig. 2. (a) Comparison of catalytic performances in various catalysts. (b) Calculated energies and electronic charge densities of the HOMO and LUMO of DPPDI, USTB-21 and USTB-22. (c) The time-dependent electronic absorption spectra of USTB-22 in DMF and Et3N. (d) The fs-TA spectra of homogeneous DPPDI radical anion excited by 700 nm laser. (e) The fs-TA spectra of USTB-21 radical anion excited by 700 nm laser. (f) The fs-TA spectra of USTB-22 radical anion excited by 700 nm laser. (g) The kinetic trace of DPPDI radical anion excited state at 570 nm. (h) The kinetic trace of USTB-21 radical anion excited state at 570 nm. (i) The kinetic trace of USTB-22 radical anion excited state at 570 nm.

Table 1 Photoreduction of various aryl halides by USTB-21 and USTB-22 a.

Entry	Conversion^b (%)	Time (h)
1	96/98	3
2	92/96	3
3	82/98	3
4	91/99	3
5	91/99	3
6	98/99	3
7	92/99	3
8	60/72	8
9	75/88	3
10	94/97	5
11	71/79	10

Table 2 Photoredox catalytic borylation by USTB-22.

Entry	Yield (%)	Time (h)
1	71	12
2	68	12
3	85	12
4	61	24
5	54	24
6	67	20
7	61	20
8^c	34	24
9	39	24

Fig. 3. (a) Proposed conPET reaction mechanism. (b) The Gibbs free energy of photocatalytic reaction based on TTF-PDI molecule as a model of USTB-22 for the reduction of 4-bromoacetophenone as an example of aryl halides.

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