[Ir₂(1-benzyl-4-(2,6-difluorophenyl)-1H-1,2,3-triazole(-1H))₄Cl₂(2-phenylpyridinato)] | 1312936-21-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [Ir₂(1-benzyl-4-(2,6-difluorophenyl)-1H-1,2,3-triazole(-1H))₄Cl₂(2-phenylpyridinato)]
• 英文别名: 1-benzyl-4-(2,4-difluorobenzene-6-id-1-yl)triazole;iridium(3+);dichloride
• CAS: 1312936-21-2
• 化学式: C₆₀H₄₀Cl₂F₈Ir₂N₁₂
• 分子量: 1536.39
• InChiKey: AOFDWMMMMGYOKW-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.29
• 重原子数：
  84
• 可旋转键数：
  8
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  123
• 氢给体数：
  0
• 氢受体数：
  22

反应信息

• 作为反应物：
  描述：

  氘代乙腈 、 [Ir₂(1-benzyl-4-(2,6-difluorophenyl)-1H-1,2,3-triazole(-1H))₄Cl₂(2-phenylpyridinato)] 以 氘代乙腈 为溶剂， 生成 N,N-trans-[Ir(1-benzyl-4-(2,4-difluorophenyl)-1H-1,2,3-triazole(1-))2(acetonitrile-d3)Cl]
  参考文献：
  名称：

  Control of the Mutual Arrangement of Cyclometalated Ligands in Cationic Iridium(III) Complexes. Synthesis, Spectroscopy, and Electroluminescence of the Different Isomers

  摘要：

  Synthetic control of the mutual arrangement of the cyclometalated ligands (C boolean AND N) in Ir(III) dimers, [Ir(C boolean AND N)(2)Cl](2), and cationic bis-cyclometalated Ir(III) complexes, [Ir(C boolean AND N)(2)-(L boolean AND L)](+) (L boolean AND L = neutral ligand), is described for the first time. Using I-benzy1-4-(2,4-difluorophenyl)-1H-1,2,3-triazole (HdfptrBz) as a cyclometalating ligand, two different Ir(III) dimers, [Ir(dfptrBz)(2)Cl](2), are synthesized depending on the reaction conditions. At 80 degrees C, the dimer with an unusual mutual cis-C,C and cis-N,N configuration of the C boolean AND N ligands is isolated. In contrast, at higher temperature (140 degrees C), the geometrical isomer with the common cis-C,C and trans-N,N arrangement of the C boolean AND N ligand is obtained. In both cases, an asymmetric bridge, formed by a chloro ligand and two adjacent nitrogens of the triazole ring of one of the cyclometalated ligands, is observed. The dimers are cleaved in coordinating solvents to give the solvent complexes [Ir(dfptrBz)(2)Cl(S)] (S = DMSO or acetonitrile), which maintain the C boolean AND N arrangement of the parent dimers. Controlling the C boolean AND N ligand arrangement in the dimers allows for the preparation of the first example of geometrical isomers of a cationic bis-cyclometalated Ir(III) complex. Thus, N,N-trans-[Ir-(dfptrBz)(2)(dmbpy)](+) (dmbpy = 4,4'-dimethyl-2,2'-bipyridine), with cis-C,C and trans-N,N arrangement of the C boolean AND N ligands, as well as N,N-cis-[Ir(dfptrBz)(2)(dmbpy)](+), with cis-C,C and cis-N,N C boolean AND N ligand orientation, are synthesized and characterized. Interestingly, both isomers show significantly different photophysical and electroluminescent properties, depending on the mutual arrangement of the C boolean AND N ligands. Furthermore, quantum chemical calculations give insight into the observed photophysical experimental data.

  DOI：

  10.1021/ja201691b
• 作为产物：
  描述：

  cis-[Ir₂(1-benzyl-4-(2,4-difluorophenyl)-1H-1,2,3-triazole^(1-))4Cl₂] 以 乙二醇乙醚 、 水 为溶剂， 生成 [Ir₂(1-benzyl-4-(2,6-difluorophenyl)-1H-1,2,3-triazole(-1H))₄Cl₂(2-phenylpyridinato)]
  参考文献：
  名称：

  Control of the Mutual Arrangement of Cyclometalated Ligands in Cationic Iridium(III) Complexes. Synthesis, Spectroscopy, and Electroluminescence of the Different Isomers

  摘要：

  Synthetic control of the mutual arrangement of the cyclometalated ligands (C boolean AND N) in Ir(III) dimers, [Ir(C boolean AND N)(2)Cl](2), and cationic bis-cyclometalated Ir(III) complexes, [Ir(C boolean AND N)(2)-(L boolean AND L)](+) (L boolean AND L = neutral ligand), is described for the first time. Using I-benzy1-4-(2,4-difluorophenyl)-1H-1,2,3-triazole (HdfptrBz) as a cyclometalating ligand, two different Ir(III) dimers, [Ir(dfptrBz)(2)Cl](2), are synthesized depending on the reaction conditions. At 80 degrees C, the dimer with an unusual mutual cis-C,C and cis-N,N configuration of the C boolean AND N ligands is isolated. In contrast, at higher temperature (140 degrees C), the geometrical isomer with the common cis-C,C and trans-N,N arrangement of the C boolean AND N ligand is obtained. In both cases, an asymmetric bridge, formed by a chloro ligand and two adjacent nitrogens of the triazole ring of one of the cyclometalated ligands, is observed. The dimers are cleaved in coordinating solvents to give the solvent complexes [Ir(dfptrBz)(2)Cl(S)] (S = DMSO or acetonitrile), which maintain the C boolean AND N arrangement of the parent dimers. Controlling the C boolean AND N ligand arrangement in the dimers allows for the preparation of the first example of geometrical isomers of a cationic bis-cyclometalated Ir(III) complex. Thus, N,N-trans-[Ir-(dfptrBz)(2)(dmbpy)](+) (dmbpy = 4,4'-dimethyl-2,2'-bipyridine), with cis-C,C and trans-N,N arrangement of the C boolean AND N ligands, as well as N,N-cis-[Ir(dfptrBz)(2)(dmbpy)](+), with cis-C,C and cis-N,N C boolean AND N ligand orientation, are synthesized and characterized. Interestingly, both isomers show significantly different photophysical and electroluminescent properties, depending on the mutual arrangement of the C boolean AND N ligands. Furthermore, quantum chemical calculations give insight into the observed photophysical experimental data.

  DOI：

  10.1021/ja201691b

文献信息

• Blue light emitting electrochemical cells incorporating triazole-based luminophores
  作者：Jesús M. Fernández-Hernández、Sébastien Ladouceur、Yulong Shen、Adriana Iordache、Xiaorong Wang、Loïc Donato、Shawn Gallagher-Duval、Manuel de Anda Villa、Jason D. Slinker、Luisa De Cola、Eli Zysman-Colman

  DOI：10.1039/c3tc31307g

  日期：——

  We report the electrochemical, photoluminescence, and electroluminescence properties of four fluorinated cationic iridium complexes bearing pyridyltriazole ancillary ligands. All the complexes display unstructured emission in the true blue region at 298 K with photoluminescent λem ranging from 452 to 487 nm in acetonitrile solution, in powder and in PMMA doped thin films. The nature of the emission is a mixed metal-to-ligand/ligand-to-ligand charge transfer state. Photoluminescence (PL) quantum efficiencies both in solution and in the solid state were low while excited state decay kinetics were found to be multiexponential. Each complex undergoes quasi-reversible oxidation and irreversible reduction with large HOMO–LUMO gaps. A detailed computational investigation corroborates the spectroscopic assignments. Additionally, light-emitting electrochemical cells (LEECs) were fabricated for each of the four complexes. The electroluminescence (EL) spectra of all complexes were red-shifted relative to the PL spectra. The LEEC containing 2a is the bluest emitter (λmax = 487 nm) of the family of complexes.

  我们报告了四种含有吡啶三唑辅助配体的氟化阳离子铱配合物的电化学、光致发光和电致发光特性。所有配合物在 298 K 的真蓝区域都显示出非结构性发射，在乙腈溶液、粉末和掺杂 PMMA 的薄膜中，光致发光 λem 为 452 至 487 nm。其发光性质为金属-配体/配体-配体混合电荷转移状态。溶液和固态中的光致发光量子效率都很低，而激发态衰减动力学是多指数的。每种复合物都经历了准可逆氧化和不可逆还原过程，具有较大的 HOMO-LUMO 间隙。详细的计算研究证实了光谱分配。此外，还为四种复合物分别制作了发光电化学电池（LEEC）。所有复合物的电致发光（EL）光谱相对于聚光光谱都发生了红移。含有 2a 的 LEEC 是复合物家族中最蓝的发光体（λmax = 487 nm）。
• Rational design and synthesis of cationic Ir(III) complexes with triazolate cyclometalated and ancillary ligands for multi-color tuning
  作者：Shao-Fen Huang、Hai-Zhu Sun、Guo-Gang Shan、Fu-Shan Li、Qun-Ying Zeng、Kai-Yue Zhao、Zhong-Min Su

  DOI：10.1016/j.dyepig.2016.12.056

  日期：2017.4

  ligand has been approved to be an excellent building block to construct efficient cationic Ir(III) dyes. Herein, a new family of Ir(III) complexes employing two different triazole fragments as cyclometalated and ancillary ligands, respectively, has been synthesized and their photophysical and electrochemical properties are investigated in detail. Through careful modification of the used ligands, efficiently

  三唑型配体已被证明是构建有效的阳离子Ir（III）染料的极好基石。本文中，已经合成了新的Ir（III）络合物家族，分别使用两个不同的三唑片段作为环金属化和辅助配体，并详细研究了它们的光物理和电化学性质。通过对使用的配体进行仔细的修饰，可以实现从深蓝色（459 nm）到红色（649 nm）的有效发射色调节，并通过综合的理论计算研究了本征结构与性质之间的关系。选择在纯膜中显示相对较高的光致发光产率的发绿光的蓝色染料3，是峰值电流效率为2.19 cd A -1的固溶处理单层器件功率效率分别为0.97 lm W -1。
• Strongly Blue Luminescent Cationic Iridium(III) Complexes with an Electron‐Rich Ancillary Ligand: Evaluation of Their Optoelectronic and Electrochemiluminescence Properties
  作者：Sébastien Ladouceur、Kalen N. Swanick、Shawn Gallagher‐Duval、Zhifeng Ding、Eli Zysman‐Colman

  DOI：10.1002/ejic.201300849

  日期：2013.10.14

  dmabpy ancillary ligands compared with those containing dtBubpy ligands. The two complexes exhibit similar electrochemical behavior. Incorporation of the dmabpy ligand shifts both the oxidation and reduction cathodically. The combination of the dmabpy and dFphtl groups increases the redox potential difference and thus the HOMO–LUMO gap but the emission is not further blueshifted. Thus, the structural

  两种强蓝色发光阳离子杂配铱配合物 1b 和 2b，带有 4,4'-双（二甲氨基）-2,2'-联吡啶（dmabpy）辅助配体和 1-苄基-4-（2,4-二氟苯基）- 1H-1,2,3-三唑 (dFphtl) 或 2-(2,4-二氟苯基)-5-甲基吡啶 (dFMeppyH) 分别已合成并充分表征。与其他类似物相比，三唑单元与 dmabpy 单元和吡啶环甲基化的相互作用就配合物的光物理、电化学和电化学发光 (ECL) 特性进行了讨论。两个复合物 1b 和 2b 是蓝色发射器，分别具有 λmax = 495 和 494 nm。激发态的性质是通过各种光物理和光化学实验以及 DFT 计算确定的。两种配合物都以配体为中心的状态发射，然而，1b 的发射具有显着的电荷转移特性，而 2b 则没有。环金属化配体上甲基的存在仅导致辐射速率常数 kr 适度增加，但与非甲基化类似物相比，不会明显影响配合物的光电特性。相比之下，当扫描到
• Iridium(III) Emitters Based on 1,4-Disubstituted-1<i>H</i>-1,2,3-triazoles as Cyclometalating Ligand: Synthesis, Characterization, and Electroluminescent Devices
  作者：Jesús M. Fernández-Hernández、Juan I. Beltrán、Vincent Lemaur、Maria-Dolores Gálvez-López、Chen-Han Chien、Federico Polo、Enrico Orselli、Roland Fröhlich、Jérôme Cornil、Luisa De Cola

  DOI：10.1021/ic3018419

  日期：2013.2.18

  analogous complexes containing the archetypal 2-(2,4-difluorophenyl)pyridinato (dfppy) as cyclometaled ligand (C∧N). Complex 2 exhibits a marked solvatochromic behavior, from 475 nm in toluene to 534 nm in formamide, due to the strong MLCT character of its emissive excited state. Complex 3 displays a true-blue emission, narrower in the visible part than FIrpic. In addition, the homoleptic complex [Ir(dfprBn)3]

  一系列基于中性双和三环金属化Ir（III）与1-苄基-4-（2,6-二氟苯基）-1 H -1,2,3-三唑（dfptrBn ）作为环金属配体被报道。该类型的双-环金属化配合物的[Ir（dfptrBn）2（L ∧ X）]用不同的辅助配体，L ∧ X =吡啶甲酸甲酯（PIC）（2）或2-（5-（全氟苯基）-2 ħ -1描述了，2,4-三唑-3-基）吡啶（pytrF 5）（3），并与包含原型2-（2,4-二氟苯基）吡啶并（dfppy）作为环金属配体的类似配合物进行了比较，比较了它们的光物理性质。 （C∧N）。复杂2由于其发射激发态具有很强的MLCT特性，因此从甲苯中的475 nm到甲酰胺中的534 nm，具有显着的溶剂变色行为。配合物3显示的是纯蓝色发射，在可见部分比FIrPIc窄。此外，均配型配合物[Ir（dfprBn）3 ]（4）中，用混合的芳基吡啶/ aryltriazole配体的杂化合物，物[Ir（dfptrBn）2（C
• Luminescent “Chugaev-type” cyclometalated iridium(III) complexes synthesized by nucleophilic addition of hydrazine
  作者：Chenggang Jiang、Louise M. Cañada、Ngoc Bao Nguyen、Thomas S. Teets

  DOI：10.1016/j.jorganchem.2022.122561

  日期：2023.1

  blue-shifted compared to previously described analogues. The complexes are synthesized by the nucleophilic addition of hydrazine to cationic bis-isocyanide iridium complexes, characterized by 1H, 13C1H}, and 19F NMR spectroscopy as well as high-resolution mass spectrometry. Four of the six molecular structures of the dicarbene complexes were determined by X-ray crystallography. Electrochemical properties

  在这项工作中，我们描述了一系列具有不同环金属化配体的六种中性 Chugaev 型螯合二卡宾铱配合物。评估了不同环金属化配体对二碳烯铱络合物发射性能的影响。三唑和 NHC 衍生的环金属化配体与提供强 σ 的 Chugaev 型二卡宾配体结合，导致与之前描述的类似物相比发生蓝移的磷光。该配合物是通过肼与阳离子双异氰化物铱配合物的亲核加成反应合成的，具有1 H、13 C 1 H} 和19F NMR 光谱以及高分辨率质谱。二卡宾络合物的六个分子结构中的四个是通过 X 射线晶体学确定的。通过循环伏安法分析评估化合物的电化学性质，这提供了 HOMO 和 LUMO 能量取决于所使用的环金属化配体的证据。所有 Chugaev 型铱配合物在 77 K 的溶液中都表现出蓝色到蓝绿色的磷光，在室温下，除了一个在聚（甲基丙烯酸甲酯）（PMMA）薄膜中外，所有的都表现出磷光。尽管所有配合物的量子产率都很低，但我们