Characterization of the Luminescent *Cu(CN)2Br2- Exciplex
Characterization of the Luminescent *Cu(CN)2Br2- Exciplex
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DOI：
10.1021/ic00101a030
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发表时间：
1994-11
影响因子：
4.6
通讯作者：
A. Horváth;Craig E. Wood;K. Stevenson
中科院分区：
文献类型：
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作者：
A. Horváth;Craig E. Wood;K. Stevenson
从某些铜（I）配合物的有效发光一直是激烈的研究的主题，特别是在分配所涉及的光学跃迁的上下文中。2· 3一方面，导致发光的铜©跃迁被归因于金属-配体电荷转移（MLCT），其中电子从铜©中心转移到配体的unoc-cu ** 轨道，4-10或电荷转移到溶剂（CTTS），其中电子电荷从中心原子移动到溶剂分子11 -13。另一方面，Cu（I）上的3d 10 - 3d 94 s和3d 10 - 3d 94 p类型的金属中心跃迁被认为是另一种发光源。所有发射的共同特征是显著的斯托克斯位移，特别是在水溶液中的卤代铜酸盐®络合物的情况下，斯托克斯位移相当大。3最近，我们证明了在二氰基铜酸盐®的水溶液中，在紫外线照射下形成的配位不饱和 * Cu（CN）2-与卤离子缔合，产生寿命更长、发光更高的物质，被指定为激基复合物。18然而，由于卤素配体也与处于基态的金属中心配位，其逐步形成常数大约比金属中心小一个数量级，
The efficient luminescence from certain Cu (I) complexes has been the subject of intense studies, particularly within the context of assigning the optical transitions involved. 2· 3 On the one hand, the copper© transitions resulting in luminescence have been ascribed to metal-to-ligand charge transfer (MLCT), where the electron is transferred from the copper© center to the unoc-cupied* orbital of the ligand, 4-10 or to charge transfer to solvent (CTTS), where the electronic charge moves to the solvent11-13 molecule from the central atom. On the other hand, a metal-centered transitions of the types 3d10— 3d94s and 3d10—3d94p on Cu (I) are considered14-17 as another source of light emission. The common feature of all of the emissions is the pronounced Stokes shift, which especially in the case of the halocuprate© complexes in aqueous solutions is rather large. 3 Recently we demonstrated that coordinatively-unsaturated* Cu (CN) 2-, formedupon UV irradiation in aqueous solutions of dicyanocuprate®, associates with halideions to create a longer-lived, more highly luminescent species assigned as an exciplex. 18 However, since halo ligands also coordinate to the metal center in the ground state, with a stepwise formation constant that is about an order of magnitude smaller than that