ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown
Published: April 3, 2025
Donor-acceptor (D-A)-type conjugated microporous polymers (CMPs) are considered promising photocatalytic materials due to their easily tunable structures and optical properties. However, the rational combination of D A units design D-A-type CMPs with efficient electron-hole separation transfer dynamics remains an ongoing challenge. Herein, we employed Density Functional Theory (DFT) calculations evaluate 16 potential D-A pair combinations respective dynamics. These consisted M-salens (M = Zn, Cu, Co, Ni) as bromine-containing monomers four alkyne-based monomers: 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (TEPT), 4,4″-diethyl-5'-(4-ethynylphenyl)-1, 1':3',1″-terphenyl (TEPB), tris(4-ethynylphenyl) amine (TEPA), 3,7-diethyl-10-(4-ethynylphenyl)-10H-phenothiazine (TEPP). Eight were obtained via DFT calculation, ranking follows: Zn-salen-TEPA > Zn-salen-TEPP Zn-salen-TEPT Cu-salen-TEPP Cu-salen-TEPA Cu-salen-TEPT Ni-salen-TEPT Co-salen-TEPT. Based on these results, three pairs exhibiting highest selected for synthesis corresponding subsequent photoelectric characterization. Experimental enhancements aligned closely predictions. Notably, aerobic oxidative amidation diverse aldehydes amines catalyzed by under blue LED irradiation achieved a yield up 97%, which surpassed performance most reported works. This work offers novel perspectives endowed highly activity.
Language: Английский