PHOSPHONITRILIC COMPOUNDS .6. HIGH MOLECULAR WEIGHT POLY(ALKOXY- AND ARYLOXPHOSPHAZENES)
PHOSPHONITRILIC COMPOUNDS .6. HIGH MOLECULAR WEIGHT POLY(ALKOXY- AND ARYLOXPHOSPHAZENES)
复制标题
DOI：
10.1021/ic50044a016
复制
发表时间：
1966-01-01
影响因子：
4.6
通讯作者：
VALAN, KJ
中科院分区：
文献类型：
--
作者：
ALLCOCK, HR;KUGEL, RL;VALAN, KJ
结论对SCOH卟啉的扩展Hück el计算未能揭示分子基态的内在不稳定性。然而，这些计算确实表明，SCOH络合物可能偏离由扩展的Hück el模型创建的“正常”过渡金属卟啉图像。在所提到的不寻常的结果中，最重要的是，通常纯的卟啉x的Eg*(X)具有很大的3DT特征，而Eg(DT)相当大地延伸到了Pporphin x体系中。到这些MO的电子跃迁既可以改变正常的x-x*卟啉光谱，又可以导致激发态，其中SC与卟啉的键大大减弱。--这项研究得到了来自一般医疗服务部的公共卫生服务研究补助金GM-10833的部分支持。计算是在哈佛大学的计算中心进行的，该中心礼貌地提供了必要的技术援助。Z.希望感谢国立卫生研究院提供的博士前奖学金。
Conclusions Extended Hückel calculations on ScOH porphin have failed to indicate any inherent instability of the molecular ground state. However, these calculations do indicate that the ScOH complex could deviate from the “normal” transition metal porphyrin picture created by the extended Hückel model. 3 Foremost among the unusual results noted is that eg*(x), normally pure porphin x, has large 3dT character, while eg (dT) extends considerably into the porphin x system. Electronic transitions to these MO’s could both alter the normal x—x* porphyrin spectrum and lead to excited states in which the Sc to porphin bonds are greatly weakened.Acknowledgments.—This research was supported in part by Public Health Service Research Grant GM-10833, from the Division of General Medical Services. The calculations were performed at the Computation Center at Harvard University, which courteously provided the necessary technical assistance.. Z. wishes to thank the National Institutes of Health for a predoctoral fellowship.