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.

中文翻译：

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三芳基硼官能化铱（III）配合物的可见光驱动制氢和聚合

新型铱（III）配合物的开发由于其高度可调节的光物理性质和广泛的应用而继续作为重要的研究领域。在本报告中，发现了三种含杂二甲二茂铁的铱（III）配合物，[Ir（p -B-ppy）₂（N ^ N）] ⁺ { p -B-ppy = 2-（4-dimesitylborylphenyl）pyridine; N ^ N = dipyrido [3,2‐ a：2'，3'‐ c ]吩嗪（dppz）（1），二吡ido基[3,2‐ d：2′，3'‐ f ]喹喔啉（dpq）（2）和1,10-菲咯啉（phen）（3）}，并进行了电化学，光物理和计算的全面表征。改变N ^ N配体的共轭长度使我们能够调整这些配合物的光物理性质，特别是它们的发光波长，可以在CH ₂ Cl ₂中将其从λ = 583调整为631 nm 。所有这三种配合物均被评估为可见光吸收增敏剂，用于从水中光生氢，并作为光催化剂，用于甲基丙烯酸甲酯的光聚合。结果表明，它们均在两种光化学反应中均具有活性。光敏剂的高活性（超过1158的营业额，其中1观察到），并且即使在20小时之后，系统也会产生氢气。此外，如果使用引发剂（例如，α-溴苯基乙酸乙酯），则可获得分子量分布相对较窄的聚（甲基丙烯酸甲酯）。在成功的扩链实验的基础上，证实了光诱导聚合反应的活性。