Ancillary Ligand Effects on Heteroleptic IrIII Dye in Dye-Sensitized Photocatalytic CO2 Reduction: Photoaccumulation of Charges on Arylated Bipyridine Ligand and Its Control on Catalytic Performance |
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Authors: | Ju Hyoung Jo Sunghan Choi Ha-Yeon Cheong Prof. Jae Yoon Shin Prof. Chul Hoon Kim Prof. Dae Won Cho Prof. Ho-Jin Son Prof. Chyongjin Pac Prof. Sang Ook Kang |
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Affiliation: | Department of Advanced Materials Chemistry, Korea University, Sejong, 30019 South Korea |
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Abstract: | Herein, we report the synthesis, and photochemical and -physical properties, as well as the catalytic performance, of a series of heteroleptic IrIII photosensitizers (IrPSs), [Ir(C^N)2(N^NAryl)]+, possessing ancillary ligands that are varied with aryl-substituents on bipyridyl unit [C^N=(2-pyridyl)benzo[b]thiophen-3-yl (btp); N^NAryl=4,4′-Y2-bpy (Y=−Ph or −PhSi(Ph)3]. We found that the π-extension of bipyridyl ligand by aryl-substitution put bipyridyl ligand in use as an electron relay unit that performed charge accumulation before delivering to the catalytic center, greatly improving the overall CO2-to-CO conversion activities. In a typical run, the aryl-substituted IrPS ( t Bu IrP-PhSi )-sensitized homogeneous systems (IrPS+ReI catalyst) gave a turnover number of 1340 (ΦCO=24.2 %) at the early stage of photolysis (<5 h). This study demonstrates that the π-character modulation on the ancillary bipyridyl ligand is critical for forthcoming catalytic performance. |
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Keywords: | intraligand electron delocalization iridium photochemical CO2 reduction photochemistry sensitizer supported catalysts |
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