SPECTRA OF PORPHYRINS
SPECTRA OF PORPHYRINS
复制标题
DOI：
10.1016/0022-2852(61)90236-3
复制
发表时间：
1961-01-01
影响因子：
1.4
通讯作者：
GOUTERMAN, M
中科院分区：
文献类型：
--
作者：
GOUTERMAN, M
本文首先介绍了三个系列的卟啉衍生自基本骨架的吸收光谱：（a）通过简单取代得到的化合物;（B）通过还原一个或多个吡咯环得到的化合物;和（c）从芳香环融合到基本骨架上得到的化合物。用四轨道模型讨论了光谱，即强度变化和能量移动与两个顶满和两个最低空π轨道的性质有关。讨论了金属卟啉的发射光谱，将其分为三个金属系列：（1）在闭壳金属中，磷光的持续增强是由于自旋-轨道耦合。(2)在顺磁性金属中，观察到的效应归因于存在一个与通常的三重态能量相同但多重性与基态相同的状态;其强度归因于交换相互作用。(3)在具有未填充壳层的抗磁性金属中，特殊的发射特性归因于低位金属三重态增强的自旋轨道耦合。最后讨论了n-π跃迁和三重态-三重态光谱。
The review opens by presenting the absorption spectra for three series of porphyrins derived from the basic skeleton: (a) compounds obtained by simple substitution; (b) compounds obtained by reduction of one or more pyrrole rings; and (c) compounds obtained from fusion of aromatic rings onto the basic skeleton. The spectra are discussed in terms of a four orbital model—that is intensity changes and energy shifts are related to the properties of two top filled and two lowest empty pi orbitals. Emission spectra of metal porphyrins are then discussed, three metal series being distinguished: (1) In closed shell metals, the continuous enhancement of phosphorescence at the expense of fluorescence is attributed to spin-orbit coupling. (2) In paramagnetic metals, observed effects are attributed to the existence of a state at the same energy as the usual triplet but with multiplicity the same as the ground state; its intensity is ascribed to exchange interactions. (3) In diamagnetic metals with unfilleddshells, peculiar emission properties are attributed to enhanced spin orbit coupling due to low lying metal triplets. The review closes by discussingn-πtransitions and triplet-triplet spectra.