Marchetti Tommaso, Rastrelli Federico, Lin Maohua, Negri Alessandro, Bonacchi Sara, Prins Leonard J, Gabrielli Luca
Dipartimento di Scienze Chimiche, Università degli studi di Padova via Marzolo 1 35131 Padova Italy
Chem Sci. 2025 Aug 29. doi: 10.1039/d5sc03858h.
While photoisomerization has dominated the design of photoswitchable catalysts, this work introduces an alternative approach: leveraging light-induced photodimerization to assemble catalytically active species. The adopted strategy is based on a acrylamidylpyrene derivative equipped with a TACN·Zn(ii) catalytic unit. This system undergoes a visible-light-induced [2 + 2] cycloaddition, which is both regioselective and reversible, to form a catalytically active photodimer. While the -to- photoisomerization of the monomer has no significant effect on catalysis, the photodimerization leads to a six-fold enhancement in catalytic activity. The photodimer's catalytic efficiency is attributed to the clustering of catalytic units, facilitating a more efficient transphosphorylation reaction. Notably, this system demonstrates the ability to temporally control catalytic reactivity, as the active dimer can be reverted to the monomers upon irradiation with UV light. This work highlights the potential of photodimerization as a robust alternative strategy for regulating catalytic activity and opens new avenues for light-responsive catalysis with temporal control.
虽然光异构化在光开关催化剂的设计中占据主导地位，但这项工作引入了一种替代方法：利用光诱导光二聚作用来组装催化活性物种。所采用的策略基于一种配备有TACN·Zn(ii)催化单元的丙烯酰胺基芘衍生物。该体系经历可见光诱导的[2 + 2]环加成反应，该反应具有区域选择性且可逆，以形成催化活性光二聚体。虽然单体的 - 到 - 光异构化对催化没有显著影响，但光二聚作用导致催化活性提高了六倍。光二聚体的催化效率归因于催化单元的聚集，促进了更有效的转磷酸化反应。值得注意的是，该体系展示了在时间上控制催化反应性的能力，因为活性二聚体在紫外光照射下可以恢复为单体。这项工作突出了光二聚作用作为调节催化活性的一种强大替代策略的潜力，并为具有时间控制的光响应催化开辟了新途径。
