[Ir(1,5-dimethyl-2,4-bis(3-methylpyrazolyl)benzene(-1H))Cl2]2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: [Ir(1,5-dimethyl-2,4-bis(3-methylpyrazolyl)benzene(-1H))Cl2]2
• 化学式: 2C₁₆H₁₇N₄*4Cl*2Ir
• 分子量: 1056.93
• InChiKey: NAZLOZZMOVJXFM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.09
• 重原子数：
  22.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  35.64
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-苯基吡啶 、 正己烷 、 二氯甲烷 、 [Ir(1,5-dimethyl-2,4-bis(3-methylpyrazolyl)benzene(-1H))Cl2]2 以 甘油 为溶剂， 以84%的产率得到[Ir(1,5-dimethyl-2,4-bis(3-methylpyrazolyl)benzene(-1H))(2-phenylpyridine(-1H))Cl]*0.5(dichloromethane)*0.5(hexane)
  参考文献：
  名称：

  Syntheses and Phosphorescent Properties of Blue Emissive Iridium Complexes with Tridentate Pyrazolyl Ligands

  摘要：

  Novel neutral mixed-ligand lr(N boolean AND C boolean AND N)(N boolean AND C)X complexes (N boolean AND C boolean AND N = 1, 3-bis (3-methylpyrazolyl)benzene (bpzb), 1,5-dimethyl-2,4-bis(3-methylpyrazolyl)benzene (dmbpzb), and 1,5-difluoro-2,4-bis(3-methylpyrazolyl)benzene (dfbpzb); N boolean AND C = 2-phenyl pyridine (ppy); and X = Cl or CN) have been synthesized and characterized. An X-ray single-crystal structure of the complex lr(dmbpzb)(ppy)Cl shows that the nitrogen atom in the ppy ligand occupied the trans position to the carbon atom in the tridentate N boolean AND C boolean AND N ligand of dmbpzb with the lr-C bond length of 1.94(1) angstrom, whereas the coordinating carbon atom occupied the trans position of chlorine. Electrochemical data show that the complexes exhibit an oxidation lr(III/IV) process in the potential range of +0.5 similar to 0.9 V and two irreversible reductions at approximately -2.6 and -3.0 V against Fc(0)/Fc(+), respectively. All of the lr(III) complexes do not emit phosphorescence at room temperature, although strong phosphorescence is exhibited at 77 K with the 0-0 transition centered at around 450 nm and lifetimes of 3-14 mu s. DFT calculations indicate that the HOMOs are mainly localized on iridium 5d pi and chlorine p pi*, whereas the LUMOs are mainly from the ppy ligand pi* orbitals. The phosphorescence originates from a (LC)-L-3 state mixed with the (MLCT)-M-3 and (XLCT)-X-3 ones. Temperature-dependent lifetime measurements of lr(dfbpzb)(ppy)Cl reveal the existence of a thermal deactivation process with a low activation energy (1720 cm(-1)) and very high frequency factor (2.3 x 10(13) s(-1)). An unrestricted density functional theory indicates that the dd state, in which both the lr-N (pyrazolyl) bond lengths increase considerably, exists almost at the same energy as that for the phosphorescent state. A thorough analysis based on the potential energy surfaces for the T-1 and S-0 states allows us to determine the reaction pathway responsible for this thermal deactivation. The calculated activation energies of 1600 similar to 1800 cm(-1) are in excellent agreement with the observed values.

  DOI：

  10.1021/ic800196s
• 作为产物：
  描述：

  氯化铱(III) 水合物 、 1,5-dimethyl-2,4-bis(3-methylpyrazolyl)benzene 以 甲醇 为溶剂， 以39%的产率得到[Ir(1,5-dimethyl-2,4-bis(3-methylpyrazolyl)benzene(-1H))Cl2]2
  参考文献：
  名称：

  Syntheses and Phosphorescent Properties of Blue Emissive Iridium Complexes with Tridentate Pyrazolyl Ligands

  摘要：

  Novel neutral mixed-ligand lr(N boolean AND C boolean AND N)(N boolean AND C)X complexes (N boolean AND C boolean AND N = 1, 3-bis (3-methylpyrazolyl)benzene (bpzb), 1,5-dimethyl-2,4-bis(3-methylpyrazolyl)benzene (dmbpzb), and 1,5-difluoro-2,4-bis(3-methylpyrazolyl)benzene (dfbpzb); N boolean AND C = 2-phenyl pyridine (ppy); and X = Cl or CN) have been synthesized and characterized. An X-ray single-crystal structure of the complex lr(dmbpzb)(ppy)Cl shows that the nitrogen atom in the ppy ligand occupied the trans position to the carbon atom in the tridentate N boolean AND C boolean AND N ligand of dmbpzb with the lr-C bond length of 1.94(1) angstrom, whereas the coordinating carbon atom occupied the trans position of chlorine. Electrochemical data show that the complexes exhibit an oxidation lr(III/IV) process in the potential range of +0.5 similar to 0.9 V and two irreversible reductions at approximately -2.6 and -3.0 V against Fc(0)/Fc(+), respectively. All of the lr(III) complexes do not emit phosphorescence at room temperature, although strong phosphorescence is exhibited at 77 K with the 0-0 transition centered at around 450 nm and lifetimes of 3-14 mu s. DFT calculations indicate that the HOMOs are mainly localized on iridium 5d pi and chlorine p pi*, whereas the LUMOs are mainly from the ppy ligand pi* orbitals. The phosphorescence originates from a (LC)-L-3 state mixed with the (MLCT)-M-3 and (XLCT)-X-3 ones. Temperature-dependent lifetime measurements of lr(dfbpzb)(ppy)Cl reveal the existence of a thermal deactivation process with a low activation energy (1720 cm(-1)) and very high frequency factor (2.3 x 10(13) s(-1)). An unrestricted density functional theory indicates that the dd state, in which both the lr-N (pyrazolyl) bond lengths increase considerably, exists almost at the same energy as that for the phosphorescent state. A thorough analysis based on the potential energy surfaces for the T-1 and S-0 states allows us to determine the reaction pathway responsible for this thermal deactivation. The calculated activation energies of 1600 similar to 1800 cm(-1) are in excellent agreement with the observed values.

  DOI：

  10.1021/ic800196s