Jabalera-Ortiz Pedro J, Rodriguez-Jimenez Alvaro M, Vismara Rebecca, Delgado Pedro, Padial Natalia M, Navarro Jorge A R, Garrido-Barros Pablo
Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Granada and Unidad de Excelencia en Química (UEQ), Avda. Fuente Nueva s/n, 18071, Granada, Spain.
ChemSusChem. 2025 Mar 4:e202500219. doi: 10.1002/cssc.202500219.
Developing excited state proton and electron donors is a promising area of research that merges the benefits of proton-coupled electron transfer (PCET) with the use of light as renewable energy input. Based on the demonstrated PCET reactivity of Zr coordination cages for reductive photocatalysis, here we synthetize and characterize a new cage with enhanced photocatalytic activity. The new design targets the extended biphenyl-4,4-dicarboxylate linker with an amino group in the meta position relative to the carboxylate. Our results show that these aspects are key to increase the stability and reduction power of the excited state, features that are typically tuned by inductive effects. As a result, the new Zr-cage promotes significantly faster PCET reactions than the previous related platform, resulting in higher chemical and quantum yields. We further showcase how the solvent can impact the photophysical properties and the PCET reaction rates depending on the cage structure. These results highlight the factors that influence excited state PCET reactivity and complement similar efforts made in the realm of H evolution.
开发激发态质子和电子供体是一个很有前景的研究领域，它将质子耦合电子转移（PCET）的优势与利用光作为可再生能源输入相结合。基于已证明的用于还原光催化的锆配位笼的PCET反应活性，我们在此合成并表征了一种具有增强光催化活性的新笼。新设计的目标是具有相对于羧酸盐处于间位的氨基的扩展联苯-4,4-二羧酸酯连接基。我们的结果表明，这些方面是提高激发态稳定性和还原能力的关键，这些特性通常通过诱导效应来调节。因此，新的锆笼比以前的相关平台显著促进更快的PCET反应，从而产生更高的化学产率和量子产率。我们进一步展示了溶剂如何根据笼结构影响光物理性质和PCET反应速率。这些结果突出了影响激发态PCET反应活性的因素，并补充了在析氢领域所做的类似工作。
