Center for Oxygen Microscopy and Imaging, Chemistry Department, Aarhus University, DK-8000, Arhus, Denmark.
J Am Chem Soc. 2010 Jun 16;132(23):8098-105. doi: 10.1021/ja101753n.
Singlet molecular oxygen, O(2)(a(1)Delta(g)), is an intermediate in a variety of oxygenation reactions. The reactivity of singlet oxygen in a given system is influenced, in part, by competitive solvent-dependent channels that deactivate singlet oxygen in a nonradiative process. It has long been considered that these deactivation channels depend only slightly on temperature. This conclusion has been incorporated into the accepted empirically derived model of electronic-to-vibrational energy transfer used to account for the effect of solvent on the lifetime of singlet oxygen, tau(Delta). The current study reveals that tau(Delta), in fact, can depend quite significantly on temperature in certain solvents (e.g., D(2)O and benzene-d(6)). These results can have practical ramifications in studies of singlet oxygen reactivity. From a fundamental perspective, these data indicate that aspects of the model for nonradiative deactivation of singlet oxygen need to be re-evaluated.
单线态氧，O(2)(a(1)Delta(g))，是多种氧合反应的中间产物。在给定体系中，单线态氧的反应活性部分受到竞争溶剂依赖性通道的影响，这些通道以非辐射过程使单线态氧失活。长期以来，人们一直认为这些失活通道几乎不受温度的影响。这一结论已被纳入用于解释溶剂对单线态氧寿命 tau(Delta)影响的接受的经验导出的电子-振动能量转移模型中。目前的研究表明，tau(Delta)实际上在某些溶剂（例如 D(2)O 和苯-d(6))中可以相当显著地依赖于温度。这些结果在研究单线态氧反应性方面具有实际意义。从根本上讲，这些数据表明需要重新评估单线态氧非辐射失活模型的某些方面。
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