Ground and Excited State Double Hydrogen Transfer in Symmetric and Asymmetric Potentials: Comparison of 2,7,12,17-Tetra-n-propylporphycene with 9-Acetoxy-2,7,12,17-tetra-n-propylporphycene
Ground and Excited State Double Hydrogen Transfer in Symmetric and Asymmetric Potentials: Comparison of 2,7,12,17-Tetra-n-propylporphycene with 9-Acetoxy-2,7,12,17-tetra-n-propylporphycene
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DOI：
10.1002/chem.201002931
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发表时间：
2011-03-01
影响因子：
4.3
通讯作者：
Waluk, Jacek
中科院分区：
文献类型：
--
作者：
Fita, Piotr;Garbacz, Piotr;Waluk, Jacek
瞬态吸收的时间分辨各向异性的分析，使确定室温下的基态和激发态速率常数的分子内双氢转移在两个类似的卟啉，其中一个与对称和其他的，与不对称的字符的双最小的潜在的氢运动。扰动在S-0中保持准对称最小值，但速率减小约两倍。在S-1中，扰动电位变得强烈不对称，并且发生下坡氢转移，其速率高于对称化合物所观察到的速率。
Analysis of time-resolved anisotropy of transient absorption enabled determination of room temperature ground and excited state rate constants for intramolecular double hydrogen transfer in two similar porphycenes, one of them with symmetric and the other, with asymmetric character of a double minimum potential for hydrogen motion. The perturbation preserves a quasi-symmetric minimum in S-0, but the rate decreases approximately two times. In S-1, the perturbed potential becomes strongly asymmetric, and the downhill hydrogen transfer occurs with a rate higher than that observed for a symmetrical compound.