取代对[Ir（ppy）<sub>2</sub>（bpy *）] PF <sub>6</sub>络合物中5,5'-二芳基-2,2'-联吡啶（bpy *）的光物理性质的作用：组合的实验和理论研究,Inorganic Chemistry

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取代对[Ir（ppy）₂（bpy *）] PF ₆络合物中5,5'-二芳基-2,2'-联吡啶（bpy *）的光物理性质的作用：组合的实验和理论研究
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2010-05-25 00:00:00 , DOI: 10.1021/ic100521t
Sébastien Ladouceur ₁ , Daniel Fortin ₁ , Eli Zysman-Colman ₁

Affiliation

据报道，合成了一个4'-官能化的5,5'-二芳基-2,2'-联吡啶（bpy *；6a - 6g）家族。这些配体与二聚体[（ppy）₂ IrCl] ₂（ppyH = 2-苯基吡啶）反应，并在随后的抗衡离子交换后提供了一系列新的发光阳离子杂原子铱（III）配合物，[（ppy）₂ Ir（ bpy *）] PF ₆（8a - 8g）。这些配合物通过电化学和光谱法表征。报道了其中两个复合物（8a和8g）的晶体结构。除8c和8f外的所有复合物在77 K和室温下，在2-MeTHF和ACN中均表现出强烈且长寿命的发射。通过计算模型将这种发射的起源指定为配体到配体电荷转移的混合物[ ³ LLCT; π（ppy）→π*（bpy *）]和金属到配体的电荷转移[ ³ MLCT; dπ（Ir）→π*（bpy *）]激发态，主要由前者组成。8a - 8c的发光性质取决于固定在二亚胺配体上的芳基取代基在4'位置的官能化，而8d - 8g的发光性质基本上是独立的，因为芳基和bpy的电子去偶联是由于取代的Ø，芳基上的邻二甲基基团，导致芳基和联吡啶基部分之间的角度接近90°。为了了解吸收光谱和发射光谱中跃迁的起源并准确预测这些配合物的发射能量，进行了密度泛函理论（DFT）/时间依赖DFT组合研究。

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Role of Substitution on the Photophysical Properties of 5,5′-Diaryl-2,2′-bipyridine (bpy*) in [Ir(ppy)2(bpy*)]PF6 Complexes: A Combined Experimental and Theoretical Study

The synthesis of a family of 4′-functionalized 5,5′-diaryl-2,2′-bipyridines (bpy*; 6a−6g) is reported. These ligands were reacted with the dimer [(ppy)₂IrCl]₂ (ppyH = 2-phenylpyridine) and afforded, after subsequent counterion exchange, a new series of luminescent cationic heteroleptic iridium(III) complexes, [(ppy)₂Ir(bpy*)]PF₆ (8a−8g). These complexes were characterized by electrochemical and spectroscopic methods. The crystal structures of two of these complexes (8a and 8g) are reported. All of the complexes except for 8c and 8f exhibit intense and long-lived emission in both 2-MeTHF and ACN at 77 K and room temperature. The origin of this emission has been assigned by computational modeling to be an admixture of ligand-to-ligand charge-transfer [³LLCT; π(ppy) → π*(bpy*)] and metal-to-ligand charge-transfer [³MLCT; dπ(Ir) → π*(bpy*)] excited states that are primarily composed of the former. The luminescent properties for 8a−8c are dependent upon the functionalization at the 4′ position of the aryl substituents affixed to the diimine ligand, while those for 8d−8g are essentially independent because of an electronic decoupling of the aryls and bpy due to the substitution of o,o-dimethyl groups on the aryls, causing a near 90° angle between the aryl and bipyridyl moieties. A combined density functional theory (DFT)/time-dependent DFT study was conducted in order to understand the origin of the transitions in the absorption and emission spectra and to predict accurately emission energies for these complexes.

更新日期：2010-05-25

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