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首页> 外文期刊>Chemistry: A European journal >Photoinduced electron transfer reactions bySmI(2) in THF: Luminescence quenching studies and mechanistic investigations
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Photoinduced electron transfer reactions bySmI(2) in THF: Luminescence quenching studies and mechanistic investigations

机译：SmI（2）在THF中的光诱导电子转移反应：发光猝灭研究和机理研究

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摘要

Photoluminescence quenching studies of SmI2 in dry THF were carried out in the presence of five different classes of compounds: ketone, alkyl chloride, nitrile, alkene and imine. The free energy change (&UDelta; G(0)) of the photoinduced electron transfer (PET) reactions was calculated from the redox potentials of the donor (SmI2) and acceptors. The bimolecular quenching constants (k(q)) derived from the Stern-Volmer experiments parallel the free energy changes of the PET processes. The observed quenching constants were compared with the theoretically derived electron transfer rate constants (k(et)) from Marcus theory and found to be in good agreement when a value of λ = 167 kJ mol(-1) (40 kcal mol(-1)) was used for the reorganization energy of the system. A careful comparison of the excited state dynamics of Sm-II in the solid state to the results obtained in solution (THF) provides new insight in to the excited states of Sm-II in THE The activation parameters determined for the PET reactions in SmI2/1-chlorobutane system are consistent with a less ordered transition state and high degree of bond reorganization in the activated complex compared to similar ground state reactions. Irradiation studies clearly show that SmI2 acts as a better reductant in the excited state and provides an alternative pathway for rate enhancement in known and novel functional group reductions.
机译：在五种不同类型的化合物（酮，烷基氯，腈，烯烃和亚胺）存在下，对无水THF中SmI2的光致发光猝灭进行了研究。从供体（SmI 2）和受体的氧化还原电势计算光诱导电子转移（PET）反应的自由能变化（ΔG（0））。从Stern-Volmer实验得到的双分子淬灭常数（k（q））与PET过程的自由能变化平行。将观察到的淬灭常数与从Marcus理论推导出的理论电子传递速率常数（k（et））进行比较，发现当λ= 167 kJ mol（-1）（40 kcal mol（-1） ））用于系统的重组能量。仔细比较固态Sm-II的激发态动力学与溶液（THF）中获得的结果，可提供对THE中Sm-II的激发态的新见解。与类似的基态反应相比，1-氯丁烷体系与活化态络合物中的有序过渡态和较高的键重组度一致。辐照研究清楚地表明，SmI2在激发态下可作为较好的还原剂，并为已知和新型官能团还原中的速率提高提供了另一种途径。

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