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Spectroscopic Study of the E /Z Photoisomerization of a New Cyrhetrenyl Acylhydrazone: A Potential Photoswitch and Photosensitizer
Photochemistry and Photobiology ( IF 2.6 ) Pub Date : 2020-07-28 , DOI: 10.1111/php.13309
Patricia M Toro 1 , Danilo H Jara 2 , A Hugo Klahn 1 , David Villaman 1 , Mauricio Fuentealba 1 , Andrés Vega 2 , Nancy Pizarro 2
Affiliation  

The new cyrhetrenyl acylhydrazone [(CO)3Re(η5‐C5H4)‐C(O)‐NH‐N = C(CH3)‐(2‐C4H2S‐5‐NO2)] (E‐CyAH) has been designed, synthesized and fully characterized to study the effect of having a cyrhetrenyl fragment (sensitizer) covalently bonded to an acylhydrazone moiety (switch), on its photophysical and photochemical properties. The crystal structure reveals that E‐CyAH adopts an E‐configuration around the iminic moiety [‐N = C(CH3)]. The absorption spectrum of E‐CyAH displays two bands at 270 and 380 nm, which are mainly ascribed to π → π* intraligand (IL) and dπ → π* metal‐to‐ligand charge transfer (MLCT) transitions, being consistent with DFT/TD‐DFT calculations. Upon 365 nm irradiation, E‐CyAH photoisomerizes to Z‐CyAH, as evidenced by UV‐Vis and 1H‐NMR spectral changes, with a quantum yield value ΦE‐CyAH →Z‐CyAH of 0.30. Z‐CyAH undergoes a first‐order thermal back‐isomerization process, with a relatively short half‐life τ1/2 of 277 min. Consequently, E‐CyAH was quantitatively recovered after 24 h, making it a fully reversible T‐type molecular photoswitch. This remarkable behavior allows us to measure the individual photophysical properties for both isomers. In addition, E‐CyAH and Z‐CyAH efficiently photosensitize the generation of singlet oxygen (O2 (1Δg)) with good yield (ΦΔ = 0.342).

中文翻译:

一种新型 Cyrhetrenyl Acylhydrazone 的 E /Z 光异构化的光谱研究:一种潜在的光开关和光敏剂

设计、合成了新的环异戊烯酰基腙[(CO)3Re(η5-C5H4)-C(O)-NH-N = C(CH3)-(2-C4H2S-5-NO2)] (E-CyAH)充分表征以研究具有共价键合到酰基腙部分(开关)的半异戊二烯基片段(敏化剂)对其光物理和光化学性质的影响。晶体结构表明 E-CyAH 在亚胺部分 [-N = C(CH3)] 周围采用 E 构型。E-CyAH 的吸收光谱在 270 和 380 nm 处显示两个带,主要归因于 π → π* 配体内(IL)和 dπ → π* 金属-配体电荷转移(MLCT)跃迁,与 DFT 一致/TD-DFT 计算。在 365 nm 照射下,E-CyAH 光异构化为 Z-CyAH,如 UV-Vis 和 1H-NMR 光谱变化所证明的那样,量子产率值 ΦE-CyAH →Z-CyAH 为 0.30。Z-CyAH 经历一级热反向异构化过程,半衰期 τ1/2 相对较短,为 277 分钟。因此,E-CyAH 在 24 小时后被定量回收,使其成为完全可逆的 T 型分子光开关。这种非凡的行为使我们能够测量两种异构体的单独光物理特性。此外,E-CyAH 和 Z-CyAH 以良好的产率(ΦΔ = 0.342)有效地光敏化单线态氧(O2(1Δg))的产生。
更新日期:2020-07-28
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