Dipartimento di Chimica G. Ciamician, Alma Mater Studiorum, Università di Bologna, via Selmi 2, 40126 Bologna, Italy.
Inorg Chem. 2010 Feb 15;49(4):1439-48. doi: 10.1021/ic901660m.
A family of new functional bis-cyclometalated thiophene-based cationic iridium complexes have been prepared and fully characterized. The introduction of formyl groups into the thienyl-based cyclometalating ligand (thpy-CHO) allows one to perform further functionalizability and to confer to the whole species potentially interesting perspectives as functional materials. The X-ray crystal structures of three complexes, namely, [Ir(thpy)(2)bpy]PF(6), [Ir(thpy-CHO)(2)bpy]PF(6), and [Ir(thpy-CHO)(2)phen]PF(6), are reported. A rich reduction voltammetric pattern of the complexes is outlined, and the effect of the substituents on the cyclic voltammetric behavior is fully elucidated. Finally, the electrochemiluminescence spectra of all of the species have been obtained in acetonitrile by annihilation of the one-electron-oxidized and -reduced forms, showing very similar features with respect to the luminescence (as both the shape and energy of the emission bands).
已经制备并充分表征了一系列新的功能性双环金属化噻吩基阳离子铱配合物。在噻吩基环金属化配体（thpy-CHO）中引入甲酰基可以进一步实现功能化，并赋予整个配合物作为功能材料的潜在有趣前景。报道了三个配合物的 X 射线晶体结构，分别为[Ir(thpy)(2)bpy]PF(6)、[Ir(thpy-CHO)(2)bpy]PF(6)和[Ir(thpy-CHO)(2)phen]PF(6)。概述了配合物丰富的还原伏安图案，并充分阐明了取代基对循环伏安行为的影响。最后，通过湮灭单电子氧化和还原形式，在乙腈中获得了所有物种的电化学发光光谱，与发光（发射带的形状和能量）相比，具有非常相似的特征。
