THE ELECTRONIC-SPECTRUM OF FE(BPY)32+ AND OS(BPY)32+
THE ELECTRONIC-SPECTRUM OF FE(BPY)32+ AND OS(BPY)32+
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DOI：
10.1021/ja00532a020
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发表时间：
1980-01-01
影响因子：
15
通讯作者：
LUDI, A
中科院分区：
文献类型：
--
作者：
DECURTINS, S;FELIX, F;LUDI, A
Fe (bpy) 32+ 和 Os (bpy) 32+ 的电子吸收光谱已在 Zn (bpy) 3S04-7H20 和 Znfbpy^ B^-óFhO 单晶中在低至 8 K 的不同温度下测定。可见光中的主要吸收强度分配给垂直于配合物 C3 轴偏振的两个不同的电荷转移跃迁，与从金属到配体的电荷转移方向一致。 Fe (bpy) 32+ 的最低能量自旋禁阻电荷转移带出现在 a 和 tt 极化中。其他 23 000 cm-1 附近的 ir 偏振吸收归因于 bpy 配体的扰动单线态到三线态跃迁。由于自旋轨道耦合的影响更大，Os (bpy) 32+ 的自旋禁戒跃迁表现出明显更高的强度和主要的极化。在其偏振态中出现向另一个三重态的自旋禁止跃迁，其起点比最低偏振三重态高 75 cm-1。假设偏振强度的机制涉及金属离子和配体之间的电子交换。
The electronic absorption spectra of Fe (bpy) 32+ and Os (bpy) 32+ have been determined in single crystals of Zn (bpy) 3S04-7H20 and Znfbpy^ B^-óFhO at various temperatures down to 8 K. The main absorption intensity in the visible is assigned to two different charge-transfer transitions polarized perpendicular to the C3 axis of the complex, consistent with the directionof charge transfer from metal to ligand. The lowest energy spin-forbidden charge-transfer bands of Fe (bpy) 32+ appear in a and tt polarization. Other ir-polarized absorption, near 23 000 cm-1, is assigned to perturbed singlet to triplet tran-sitions of the bpy ligand. Owing to the much greater influence of spin-orbit coupling, the spin-forbidden transitions ofOs (bpy) 32+ show significantly higher intensitiesand predominant polarization. A spin-forbidden transition to another triplet state appears in it polarization, its origin lying 75 cm-1 higher than the lowest-polarized triplet state. The mechanism for the-polarized intensity is assumed to involve electron exchange between metal ion and ligands.