Heterochelates of ruthenium(II): electrochemistry, absorption spectra, and luminescence properties
Heterochelates of ruthenium(II): electrochemistry, absorption spectra, and luminescence properties
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DOI：
10.1016/s0277-5387(97)00174-5
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发表时间：
1997-01-01
期刊：
影响因子：
2.6
通讯作者：
Adhikary, B
中科院分区：
文献类型：
--
作者：
Baitalik, S;Adhikary, B
合成并表征了邻氨基苯酚与对位取代苯甲醛Schiff碱配体[Ru（bpy）（2）（L-X）]（ClO_4）（1-6）的配合物HL-X（X= NO_2，Cl，F，Me，OMe和NMe_2）。除6（X= NMe 2）外，所有配合物的循环伏安图均表现出可逆的Ru-II/Ru-III和不可逆的Ru-III/Ru-IV氧化过程。在6的情况下，两个氧化过程都可逆地发生。通过绘制Ru-II/Ru-III电偶的E-1/2值与Hammett σ（+）参数的关系图，获得线性相关性。配合物的吸收光谱相似，显示出由于d pi-pi（*）（bpy）、Schiff碱n-pi（*）和pi-pi（*）配体内跃迁引起的吸收带。还获得了（v）与bar（max）（MLCT）和Delta E-1/2（第一氧化和第一还原对之间的分离）之间的线性相关性。研究了溶剂对MLCT和n-pi（*）吸收带的影响。荧光光谱研究表明，所有的配合物在室温下发光，所观察到的发射带是由于金属扰动配体为中心的跃迁。(C)1997 Elsevier Science Ltd.
A series of heterochelates [Ru(bpy)(2)(L-X)](ClO4) (1-6) derived from the schiff bases of o-aminophenol and p-substituted (X) benzaldehydes, HL-X (X=NO2, Cl, F, Me, OMe and NMe2) have been synthesized and characterized. Cyclic voltammograms of all the complexes, except 6 (X=NMe2), exhibit a reversible Ru-II/Ru-III and an irreversible Ru-III/Ru-IV oxidation processes. In the case of 6, both the oxidation process take place reversibly. A linear correlation is obtained by plotting the E-1/2, value of Ru-II/Ru-III couple against the Hammett sigma(+) parameters. The absorption spectra of the complexes are similar showing absorption bands due to d pi-pi(*) (bpy), Schiff base n-pi(*) and pi-pi(*) intraligand transitions. A linear correlation is also obtained between (v) over bar(max) (MLCT) and Delta E-1/2 (separation between the first oxidation and first reduction couples). The effect of solvents on the MLCT and n-pi(*) absorption bands have been studied. Fluorescent spectral studies have shown that all the complexes luminesce at room temperature and the observed emission bands are due to metal-perturbed ligand-centred transitions. (C) 1997 Elsevier Science Ltd.