Alemayehu Abraham B, Conradie Jeanet, Larsen Simon, Pérez Bjørn Cicerôn Lukas, Settineri Nicholas S, Ghosh Abhik
Department of Chemistry, UiT - The Arctic University of Norway, Tromsø N-9037, Norway.
Department of Chemistry, University of the Free State, P.O. Box 339, Bloemfontein 9300, Republic of South Africa.
Inorg Chem. 2025 Jun 23;64(24):12242-12253. doi: 10.1021/acs.inorgchem.5c01593. Epub 2025 Jun 9.
Following the successful synthesis of rhenium-oxido, rhenium-imido, and rhenium-sulfido corroles, a series of -X-substituted rhenium-selenido triarylcorroles (X = OCH, CH, H, F, CF) have been prepared in 70-76% yields. A one-pot, two-step procedure was used, analogous to that used for ReS corroles, involving rhenium insertion via high-temperature reaction of Re(CO) and free-base corroles in refluxing decalin, followed by exposure to PCl (which is thought to deoxygenate ReO corroles formed under the reaction) and elemental selenium. An analogous procedure, however, failed to yield rhenium-tellurido corroles, presumably reflecting, according to DFT calculations, the limited stability of these species. Unlike ReO corroles, ReS and ReSe corroles were found not to exhibit phosphorescence in the NIR-I regime (600-1000 nm); nor did they sensitize singlet oxygen formation. In the hope of obtaining a broader perspective of this negative result, we also examined ReN porphyrins and found them not to phosphoresce or to sensitize singlet oxygen formation. These results were explained by DFT and TDDFT calculations in terms of low-energy triplet states, which are not energetic enough to excite molecular oxygen to its lowest singlet state. Whether some of the new Re corroles exhibit phosphorescence in the NIR-II regime remains an interesting question for future investigation .
在成功合成氧化铼、亚胺基铼和硫化铼卟啉之后，已通过一锅两步法以70 - 76%的产率制备了一系列 -X-取代的硒化铼三芳基卟啉（X = OCH、CH、H、F、CF）。该方法类似于用于制备ReS卟啉的方法，包括通过在回流的十氢化萘中使Re(CO)与游离碱卟啉进行高温反应插入铼，随后暴露于PCl（据认为其可使反应中形成的ReO卟啉脱氧）和元素硒。然而，类似的方法未能制得碲化铼卟啉，根据密度泛函理论（DFT）计算推测，这可能反映出这些物种的稳定性有限。与ReO卟啉不同，发现ReS和ReSe卟啉在近红外I区（600 - 1000 nm）不表现出磷光；它们也不敏化单线态氧的形成。为了更全面地了解这一负面结果，我们还研究了ReN卟啉，发现它们也不发磷光或敏化单线态氧的形成。这些结果通过DFT和含时密度泛函理论（TDDFT）计算，从低能三重态的角度进行了解释，这些三重态的能量不足以将分子氧激发到其最低单线态。一些新型Re卟啉是否在近红外II区表现出磷光仍是未来研究中一个有趣的问题。
