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Tris-heteroleptic Iridium Complexes Based on Cyclometalated Ligands with Different Cores
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-09-18 00:00:00 , DOI: 10.1021/acs.inorgchem.7b01307 Yanouk Cudré 1 , Felipe Franco de Carvalho 2 , Gregory R. Burgess 1 , Louise Male 1 , Simon J. A. Pope 3 , Ivano Tavernelli 4 , Etienne Baranoff 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-09-18 00:00:00 , DOI: 10.1021/acs.inorgchem.7b01307 Yanouk Cudré 1 , Felipe Franco de Carvalho 2 , Gregory R. Burgess 1 , Louise Male 1 , Simon J. A. Pope 3 , Ivano Tavernelli 4 , Etienne Baranoff 1
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A series of tris-heteroleptic iridium complexes of the form [Ir(C^N1)(C^N2)(acac)] combining 2-phenylpyridine (ppy), 2-(2,4-difluorophenyl)pyridine (dFppy), 1-phenylpyrazole (ppz), and 1-(2,4-difluorophenyl)pyrazole (dFppz) as the C^N ligands have been synthesized and fully characterized by NMR, X-ray crystallography, UV–vis absorption and emission spectroscopy, and electrochemical methods. It is shown that “static properties” (e.g., absorption and emission spectra and redox potentials) are primarily dictated by the overall architecture of the complex, while “dynamic properties” (e.g., excited-state lifetime and radiative and nonradiative rate constants) are, in addition, sensitive to the specific positioning of the substituents. As a result, the two complexes [Ir(dFppy)(ppz)(acac)] and [Ir(ppy)(dFppz)(acac)] have the same emission maxima and redox potentials, but their radiative and nonradiative rate constants differ significantly by a factor ∼2. Then acetylacetonate (acac) was replaced by picolinate (pic), and two pairs of diastereoisomers were obtained. As expected, the use of pic as the ancillary ligand results in blue-shifted emission, stabilization of the oxidation potential, and improvement of the photoluminescence quantum yield, and only minor differences in the optoelectronic properties are found between the two diastereoisomers of each pair.
中文翻译：
基于不同核的环金属化配体的三杂铱铱配合物
[Ir（C ^ N 1）（C ^ N 2）形式的一系列三杂铱铱配合物）（acac）]将2-苯基吡啶（ppy），2-（2,4-二氟苯基）吡啶（dFppy），1-苯基吡唑（ppz）和1-（2,4-二氟苯基）吡唑（dFppz）合并已经合成了C ^ N配体，并已通过NMR，X射线晶体学，UV-vis吸收和发射光谱以及电化学方法进行了全面表征。结果表明，“静态特性”（例如，吸收和发射光谱以及氧化还原电势）主要由配合物的整体结构决定，而“动态特性”（例如，激发态寿命以及辐射和非辐射速率常数）是此外，对取代基的具体位置敏感。结果，两个络合物[Ir（dFppy）（ppz）（acac）]和[Ir（ppy）（dFppz）（acac）]具有相同的发射最大值和氧化还原电位，但是它们的辐射速率常数和非辐射速率常数相差约2倍。然后将乙酰丙酮酸酯（acac）替换为吡啶甲酸酯（pic），得到两对非对映异构体。如预期的那样，使用pic作为辅助配体会导致蓝移发射，氧化电位的稳定和光致发光量子产率的提高，并且在每对的两个非对映异构体之间仅发现了很小的光电特性差异。
更新日期：2017-09-18
中文翻译：
基于不同核的环金属化配体的三杂铱铱配合物
[Ir（C ^ N 1）（C ^ N 2）形式的一系列三杂铱铱配合物）（acac）]将2-苯基吡啶（ppy），2-（2,4-二氟苯基）吡啶（dFppy），1-苯基吡唑（ppz）和1-（2,4-二氟苯基）吡唑（dFppz）合并已经合成了C ^ N配体，并已通过NMR，X射线晶体学，UV-vis吸收和发射光谱以及电化学方法进行了全面表征。结果表明，“静态特性”（例如，吸收和发射光谱以及氧化还原电势）主要由配合物的整体结构决定，而“动态特性”（例如，激发态寿命以及辐射和非辐射速率常数）是此外，对取代基的具体位置敏感。结果，两个络合物[Ir（dFppy）（ppz）（acac）]和[Ir（ppy）（dFppz）（acac）]具有相同的发射最大值和氧化还原电位，但是它们的辐射速率常数和非辐射速率常数相差约2倍。然后将乙酰丙酮酸酯（acac）替换为吡啶甲酸酯（pic），得到两对非对映异构体。如预期的那样，使用pic作为辅助配体会导致蓝移发射，氧化电位的稳定和光致发光量子产率的提高，并且在每对的两个非对映异构体之间仅发现了很小的光电特性差异。
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