Nelsen Stephen F, Schultz Kevin P
Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706-1396, USA.
J Phys Chem A. 2009 May 14;113(19):5577-84. doi: 10.1021/jp811433p.
Kinetics for intramolecular charge transfer between two diarylhydrazine units, measured by ESR, are reported for six charge-localized mixed valence compounds having 9, 11, 13, and 16 bonds between the nitrogen atoms. A 17-bond bridged compound had too slow electron transfer to measure the rate constant by ESR. The optical spectra of these radical cations are compared with tert-butyl,aryl-substituted hydrazines, and rate constants calculated using parameters derived from the optical spectra are compared with the experimental values where possible. The charge-transfer band overlapped too badly with bridge-centered absorption for the 16-bond bridged compound to allow the comparison to be made. The 13-bond bridged compound gave worse agreement than the other compounds. Its optical rate constant was about 5.4 times the ESR rate constant at a temperature between the ranges in which the data were collected.
通过电子自旋共振（ESR）测量了六个在氮原子之间具有9、11、13和16个键的电荷定域混合价化合物中两个二芳基肼单元之间分子内电荷转移的动力学。一个具有17个键桥连的化合物电子转移太慢，无法通过ESR测量速率常数。将这些自由基阳离子的光谱与叔丁基芳基取代的肼进行了比较，并在可能的情况下，将使用从光谱得出的参数计算的速率常数与实验值进行了比较。对于具有16个键桥连的化合物，电荷转移带与桥中心吸收重叠过于严重，无法进行比较。具有13个键桥连的化合物比其他化合物的吻合度更差。在收集数据的温度范围内，其光学速率常数约为ESR速率常数的5.4倍。
