Visible‐Light‐Driven Hydrogen Production and Polymerization using Triarylboron‐Functionalized Iridium(III) Complexes |
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| Authors: | Ling‐Xia Yang Wan‐Fa Yang Yong‐Jun Yuan Yi‐Bing Su Miao‐Miao Zhou Xiao‐Le Liu Guang‐Hui Chen Xin Chen Zhen‐Tao Yu Zhi‐Gang Zou |
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| Affiliation: | 1. National Laboratory of Solid State Microstructures and Collaborative Innovation Center of Advanced Microstructures, Jiangsu Provincial Key Laboratory for Nanotechnology, College of Engineering and Applied Sciences, Nanjing University, Nanjing, Jiangsu, China;2. National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences, Shanghai, China;3. College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou, Zhejiang, China;4. Department of Chemistry, Shantou University, Guangdong, China |
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| Abstract: | The development of novel iridium(III) complexes has continued as an important area of research owing to their highly tunable photophysical properties and versatile applications. In this report, three heteroleptic dimesitylboron‐containing iridium(III) complexes, [Ir(p‐B‐ppy)2(N^N)]+ {p‐B‐ppy=2‐(4‐dimesitylborylphenyl)pyridine; N^N=dipyrido[3,2‐a:2′,3′‐c]phenazine (dppz) ( 1 ), dipyrido[3,2‐d:2′,3′‐f]quinoxaline (dpq) ( 2 ), and 1,10‐phenanthroline (phen) ( 3 )}, were prepared and fully characterized electrochemically, photophysically, and computationally. Altering the conjugated length of the N^N ligands allowed us to tailor the photophysical properties of these complexes, especially their luminescence wavelength, which could be adjusted from λ=583 to 631 nm in CH2Cl2. All three complexes were evaluated as visible‐light‐absorbing sensitizers for the photogeneration of hydrogen from water and as photocatalysts for the photopolymerization of methyl methacrylate. The results showed that all of them were active in both photochemical reactions. High activity for the photosensitizer (over 1158 turnover numbers with 1 ) was observed, and the system generated hydrogen even after 20 h. Additionally, poly(methyl methacrylate) with a relatively narrow molecular‐weight distribution was obtained if an initiator (i.e., ethyl α‐bromophenylacetate) was used. The living character of the photoinduced polymerization was confirmed on the basis of successful chain‐extension experiments. |
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| Keywords: | hydrogen iridium photocatalysis polymerization sensitizers |
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